U.S. patent number 4,938,796 [Application Number 07/208,269] was granted by the patent office on 1990-07-03 for herbicidal compositions of acylated 1,3-dicarbonyl herbicides and antidotes therefor.
This patent grant is currently assigned to ICI Americas Inc.. Invention is credited to Lawrence L. Buren, Charles J. Duerksen, Michael P. Ensminger, Joanna K. Hsu, Nicholas N. Poletika, Benjamin P. Rodriquez.
United States Patent |
4,938,796 |
Buren , et al. |
July 3, 1990 |
**Please see images for:
( Certificate of Correction ) ** |
Herbicidal compositions of acylated 1,3-dicarbonyl herbicides and
antidotes therefor
Abstract
This invention embodies a two-part herbicidal system comprised
of an acylated 1,3-dicarbonyl herbicide compound corresponding to
the formula ##STR1## and tautomeric forms thereof wherein R is an
aromatic moiety, optionally substituted, and a non-phytotoxic
antidotally effective amount of an antidote therefor selected from
the group of amides of haloalkanoic acids, including oxazolidines
and thiazolidines, aromatic oxime derivatives, thiazole carboxylic
acids and derivatives, and 1,8-naphthalic anhydride.
Inventors: |
Buren; Lawrence L. (Cupertino,
CA), Hsu; Joanna K. (Sunnyvale, CA), Ensminger; Michael
P. (San Jose, CA), Duerksen; Charles J. (Visalia,
CA), Poletika; Nicholas N. (Visalia, CA), Rodriquez;
Benjamin P. (Visalia, CA) |
Assignee: |
ICI Americas Inc. (Wilmington,
DE)
|
Family
ID: |
26750670 |
Appl.
No.: |
07/208,269 |
Filed: |
June 22, 1988 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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70015 |
Jul 6, 1987 |
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Current U.S.
Class: |
504/239; 504/242;
504/243; 504/178; 504/191; 504/177 |
Current CPC
Class: |
A01N
37/42 (20130101); A01N 41/10 (20130101); A01N
43/54 (20130101); A01N 35/06 (20130101); A01N
43/16 (20130101); A01N 43/18 (20130101); A01N
35/10 (20130101); A01N 43/40 (20130101); A01N
35/06 (20130101); A01N 25/32 (20130101); A01N
35/10 (20130101); A01N 25/32 (20130101); A01N
43/40 (20130101); A01N 25/32 (20130101); A01N
43/16 (20130101); A01N 25/32 (20130101); A01N
43/18 (20130101); A01N 25/32 (20130101); A01N
43/54 (20130101); A01N 25/32 (20130101); A01N
41/10 (20130101); A01N 25/32 (20130101); A01N
37/42 (20130101); A01N 25/32 (20130101); A01N
35/06 (20130101); A01N 2300/00 (20130101); A01N
35/10 (20130101); A01N 2300/00 (20130101); A01N
37/42 (20130101); A01N 2300/00 (20130101); A01N
41/10 (20130101); A01N 2300/00 (20130101); A01N
43/16 (20130101); A01N 2300/00 (20130101); A01N
43/18 (20130101); A01N 2300/00 (20130101); A01N
43/40 (20130101); A01N 2300/00 (20130101); A01N
43/54 (20130101); A01N 2300/00 (20130101) |
Current International
Class: |
A01N
41/00 (20060101); A01N 43/16 (20060101); A01N
43/02 (20060101); A01N 43/48 (20060101); A01N
43/40 (20060101); A01N 35/06 (20060101); A01N
35/10 (20060101); A01N 35/00 (20060101); A01N
43/18 (20060101); A01N 37/42 (20060101); A01N
41/10 (20060101); A01N 43/34 (20060101); A01N
43/54 (20060101); A01N 035/06 (); A01N 041/10 ();
A01N 041/12 () |
Field of
Search: |
;71/98,123,88 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1192758 |
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Sep 1985 |
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CA |
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0090262 |
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May 1983 |
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EP |
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0186118 |
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Jul 1986 |
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EP |
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2350547 |
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Apr 1974 |
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DE |
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51-113755 |
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Feb 1976 |
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JP |
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51-13750 |
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Mar 1976 |
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JP |
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2023582 |
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Mar 1980 |
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GB |
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Primary Examiner: Raymond; Richard L.
Assistant Examiner: Bembenick; Brian
Attorney, Agent or Firm: Polyn; Denis A.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of application Ser. No.
070,015, filed July 6, 1987, now abandoned.
Claims
What is claimed is:
1. A herbicide composition wherein said herbicidally active
ingredient is a compound of the formula ##STR49## in which R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are independently
hydrogen, halogen or C.sub.1 -C.sub.4 alkyl
or in which R.sup.1 and R.sup.2, or R.sup.3 and R.sup.4, taken
together are C.sub.2 -C.sub.5 alkylene;
R.sub.7 is halogen; C.sub.1 -C.sub.4 alkyl; or nitro;
R.sup.8, R.sup.9, and R.sup.10 independently are hydrogen or
substituants including halogen; C.sub.1 -C.sub.4 alkyl; C.sub.1
-C.sub.4 alkoxy; trifluoromethoxy; C.sub.1 -C.sub.4 haloalkyl
R.sub.b S(O).sub.n in which n is 0, 1 or 2; and R.sub.b is C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, phenyl or benzyl;
and as an antidote compound therefor, a nonphytotoxic antidotally
effective amount of a compound selected from amides of haloalkanoic
acids; and 1,8 naphthalic anhydride, wherein said compound is
antidotally active with said herbicide and wherein the weight ratio
of herbicide to antidote is from about 0.0:1 to about 30:1.
2. A herbicide composition as defined in claim 1 wherein said
antidote is an amide of haloalkanoic acid.
3. A herbicide composition as defined in claim 2 wherein said
haloalkanoic acid is dichloroacetic acid.
4. A herbicide composition as defined in claim 2 wherein said
antidote is an amide wherein the nitrogen atom thereof is in an
oxazolidine.
5. A herbicide composition as defined in claim 1 wherein said
antidote is 1,8-naphthalic anhydride.
6. A herbicide composition as defined in claim 1 wherein said
antidote compounds correspond to the formula ##STR50## in which n
is 1 or 2, Y is chlorine or bromine and R.sup.8' and R.sup.9' are
independently C.sub.1 -C.sub.12 alkyl, C.sub.2 -C.sub.12 alkenyl,
dialkoxyalkyl wherein the alkoxy and alkyl groups each have 1-4
carbon atoms and R.sup.8' and R.sup.9' taken together are C.sub.1
-C.sub.4 alkyleneoxy alkylene.
7. A herbicide composition as defined in claim 1 wherein said
antidote compounds correspond to the formula ##STR51## wherein
formula, R.sup.80, R.sup.81, R.sup.82, R.sup.83, R.sup.84 and
R.sup.85 are independently hydrogen, lower alkyl, or R.sup.80 and
R.sup.81 taken together form a alkylene group; and X is oxygen or
sulfur optionally substituted by one or two methyl groups and X is
oxygen or sulfur.
8. A herbicide composition as defined in claim 1 wherein said
herbicidal active ingredient is a compound of the formula ##STR52##
wherein R.sup.70 is halogen; C.sub.1 -C.sub.2 alkyl; nitro
R.sup.71 is hydrogen or C.sub.1 -C.sub.4 alkyl; or halogen
R.sup.72 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.71 and R.sup.72 together are C.sub.2 -C.sub.5 alkylene;
R.sup.73 is hydrogen; C.sub.1 -C.sub.4 alkyl
R.sup.74 is hydrogen; C.sub.1 -C.sub.4 alkyl;
R.sup.75 is hydrogen; halogen or C.sub.1 -C.sub.4 alkyl;
R.sup.76 is halogen, nitro, cyano, trifluoromethyl, and
R.sup.77 and R.sup.78 independently are (1) hydrogen; (2) halogen;
(3) C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5)
trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4
haloalkyl.
9. A method of reducing injury to crops by a herbicide of the
formula ##STR53## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5 and R.sup.6 are independently hydrogen or C.sub.1 -C.sub.4
alkyl or
in which R.sup.1 and R.sup.2 , or R.sup.3 and R.sup.4, taken
together are C.sub.2 -C.sub.5 alkylene;
R.sup.7 is nitro;
R.sup.8, R.sup.9 and R.sup.10 independently are hydrogen or
substituants including halogen; C.sub.1 -C.sub.4 alkyl; C.sub.1
-C.sub.4 alkoxy; trifluoromethoxy; C.sub.1 -C.sub.4 haloalkyl;
which comprises applying to the soil, crop or seed crop a
non-phytotoxic antidotally effective amount of a compound selected
from the group consisting of amides of haloalkanoic acids, wherein
said compound is antidotally active with said herbicide and wherein
the weight ratio of herbicide to antidote compound is from about
0.1:1 to about 30:1.
10. The method of claim 8 wherein said method is a seal
treatment.
11. The method of claim 8 wherein said method is a soil
incorporation treatment.
12. The method of claim 9 wherein said antidote is an amide of
haloalkanoic acid.
13. The method of claim 12 wherein said haloalkanoic acid is
dichloroacetic acid.
14. The method of claim 9 wherein said antidote is an amide of
haloalkanoic acid wherein the nitrogen atom is in an
oxazolidine.
15. The method of reducing injury to crops as defined in claim 9
wherein said herbicide is of the formula ##STR54## in which
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are
independently hydrogen or C.sub.1 -C.sub.4 alkyl;
or in which R.sup.1 and R.sup.2, or R.sup.3 and R.sup.4, taken
together are C.sub.2 -C.sub.5 alkylene;
R.sub.7 is nitro;
R.sup.8, R.sup.9 and R.sup.10 independently are hydrogen or
substituents including halogen; C.sub.1 -C.sub.4 alkyl; C.sub.1
-C.sub.4 alkoxy; trifluoromethoxy; C.sub.1 -C.sub.4 haloalkyl;
and said antidote compound corresponds to the formula ##STR55## in
which n is 1 or 2, Y is chlorine or bromine and R.sup.8' and
R.sup.9' are independently C.sub.1 -C.sub.12 alkyl, C.sub.2
-C.sub.12 alkylene, dialkoxyalkyl wherein the alkoxy and alkyl
groups each have 1-4 carbon atoms and R.sup.8' and R.sup.9' taken
together are C.sub.1 -C.sub.4 alkyleneoxy alkylene.
16. The method of reducing injury to crops as defined in claim 9
wherein said herbicide is of the formula ##STR56## in which
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are
independently hydrogen or C.sub.1 -C.sub.4 alkyl;
or in which R.sup.1 and R.sup.2, or R.sup.3 and R.sup.4, taken
together are C.sub.1 -C.sub.4 alkylene;
R.sub.7 is nitro;
R.sup.8, R.sup.9 and R.sup.10 independently are hydrogen or
substituents including halogen; C.sub.1 -C.sub.4 alkyl; C.sub.1
-C.sub.4 alkoxy; trifluoromethoxy; C.sub.1 -C.sub.4 -haloalkyl
and said antidote compound corresponds to the formula ##STR57##
wherein R.sup.80, R.sup.81, R.sup.82, R.sup.83, R.sup.84 and
R.sup.85 are independently hydrogen, lower alkyl or R.sup.80 and
R.sup.81 taken together form a alkylene group; and X is oxygen
optionally substituted by one or two methyl groups.
17. The method of reducing injury to crops as defined in claim 9
wherein said herbicide is of the formula ##STR58## wherein R.sup.70
is nitro;
R.sup.71 is hydrogen, C.sub.1 -C.sub.4 alkyl or halogen;
R.sup.72 is hydrogen or C.sub.1 -C.sub.4 alkyl; or
R.sup.71 and R.sup.72 taken together are C.sub.2 -C.sub.5
alkylene;
R.sup.73 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.74 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.75 is hydrogen, halogen or C.sub.1 -C.sub.4 alkyl;
R.sup.76 is halogen, nitro, cyano, trifluoromethyl;
R.sup.77 and R.sup.78 independently are (1) hydrogen; (2) halogen;
(3) C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5)
trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4
haloalkyl.
18. The composition of claim 1 wherein said acylated 1,3-dicarbonyl
compound contains from about 11 carbon atoms to about 42 carbon
atoms, inclusive.
19. The method of claim 9 wherein said acylated 1,3-dicarbonyl
compound contains from about 11 carbon atoms to about 42 carbon
atoms, inclusive.
20. The method of claim 9 wherein said method is a preemergence
treatment.
21. The method of claim 9 wherein said method is a surface
treatment.
Description
FIELD OF THE INVENTION
This invention relates to herbicide compositions and methods of
use, and more particularly, to certain herbicidal compositions
comprising substituted acylated 1,3-dicarbonyl compounds and
antidotes therefor which are useful as herbicides.
BACKGROUND OF THE INVENTION
An herbicide is a compound which adversely controls or modifies
plant growth, e.g., killing, retarding, defoliating, desiccating,
regulating, stunting, tillering, stimulating and dwarfing. The term
"plant" refers to all physical parts of a plant, including seeds,
seedlings, saplings, roots, tubers, stems, stalks, foliage, and
fruits. "Plant growth" includes all phases of development from seed
germination to natural or induced cessation of life.
Herbicides are generally used to control or eradicate weed pests.
They have gained a high degree of commercial success because it has
been shown that such control can increase crop yield and reduce
harvesting costs.
The most popular methods of herbicide application include: preplant
incorporation into the soil; in-furrow application to seeds and
surrounding soil; pre-emergence surface treatment of seeded soil;
post-emergence treatment of the plant and soil; and preplant seed
treatment.
A manufacturer of an herbicide generally recommends a range of
application rates and concentrations calculated to maximize weed
control. The range of rates varies from approximately 0.01 to 50
pounds per acre (0.0111 to 56 kilograms per hectare [Kg/ha]), and
is usually in the range of from 0.1 to 25 pounds per acre (0.112 to
28 Kg/ha). The term "herbicidally effective amount" describes an
amount of an herbicide compound which adversely controls or
modifies plant growth. The actual amount used depends upon several
considerations, including particular weed susceptibility and
overall cost limitations.
An important factor influencing the usefulness of a given herbicide
is its selectivity towards crops. In some cases, a beneficial crop
is susceptible to the effects of the herbicide. In addition,
certain herbicidal compounds are phytotoxic to some weed species
but not to others. To be effective, an herbicide must cause minimal
damage (preferably no damage) to the beneficial crop while
maximizing damage to weed species which infest the locus of the
crop.
To preserve the beneficial aspects of herbicide use and to minimize
crop damage, many herbicide antidotes have been prepared. These
antidotes reduce or eliminate damage to the crop without
substantially impairing the damaging effect of the herbicide on
weed species. See, for example, U.S. Pat. Nos. 4,021,224, 4,021,229
and 4,230,874.
The precise mechanism by which an antidote reduces herbicidal crop
injury has not been established. An antidote compound may be a
remedy, interferent, protectant, or antagonist. As used herein,
"antidote" describes a compound which has the effect of
establishing herbicide selectivity, i.e., continue herbicidal
phytotoxicity to weed species by the herbicide, and reduced or
non-phytotoxicity to the cultivated crop species. The term
"antidotally effective amount" describes an amount of an antidote
compound which counteracts to some degree a phytotoxic response of
a beneficial crop to an herbicide.
Acylated 1,3-dicarbonyl compounds have been found to be very
effective herbicides with broad general herbicidal activity against
a wide range of plant species. The method of controlling vegetation
with the compounds comprises applying an herbicidally effective
amount of the compounds, usually with an inert carrier, to the area
where herbicidal control is desired. However, the herbicidal
acylated 1,3-dicarbonyl compounds have been found in some instances
to adversely affect or interfere with the cultivation of a variety
of crops. Therefore, the effective use of these herbicides for
controlling weeds in the presence of such crops is further enhanced
by, or may require in many instances, the addition of an
antidotally effective amount of a compound, which is antidotally
effective with the herbicide.
DESCRIPTION OF THE INVENTION
It has now been discovered that certain compounds when used in an
antidotally effective amount are effective antidotes for the
protection of a variety of crops from adverse herbicidal injury or
the reduction of adverse herbicidal injury caused by the use of an
herbicidally effective amount of an acylated 1,3-dicarbonyl
carbocyclic or heterocyclic herbicidal compound.
DESCRIPTION OF THE HERBICIDE COMPOUNDS
The acylated 1,3-dicarbonyl herbicide compounds of this invention
are contained within and correspond to the following general
formula ##STR2## in which R is a group as hereinafter defined (and
may generally be an optionally substituted aromatic moiety).
Compounds of this type have been described in a number of
references as being useful, for instance, as chemical intermediates
and/or pesticides. The undefined remainder of the molecule
represented in Formula A, which includes the dicarbonyl group, has
a generally cyclical structure. In particular, the cyclical
structure which is the cyclical 1,3-dicarbonyl group including a 5-
to 6-member ring, which may be carbocyclic or heterocyclic which
may be further optionally substituted with one or more aromatic
groups.
Tautomerism is possible in the herbicide carbocyclic or
heterocyclic compounds of this invention. For example, the cyclic
1,3-dicarbonyl containing herbicide compounds of this invention can
have the following four structural formulae because of tautomerism:
##STR3## wherein the undefined substituents are as defined
hereinafter. Similar tautomerism is observed for corresponding
heterocyclic compounds.
The circled proton on each of the four tautomers is reasonably
labile. These protons are acidic and can be removed by a base to
give a salt having an anion of the following four resonant forms
##STR4## wherein the undefined further substituents are as herein
below defined.
Examples of cations of these bases are inoganic cations such as
alkali metals, e.g. lithium, sodium, and potassium, alkaline earth
metals, e. g. barium, magnesium, calcium and strontium, or organic
cations such as substituted ammonium sulfonium or phosphonium
wherein the substituent is an aliphatic or aromatic group.
Acylated carbocyclic 1,3-dicarbonyl compounds of this type have the
general structure ##STR5## in which R is an optionally substituted
aromatic moiety as hereinafter defined and n is 2 or 3, preferably
3. The ring can be unsubstituted (all X and Y groups are hydrogen),
or one or more hydrogen atoms may be replaced by aliphatic,
aromatic, heterocyclic or alkylene groups, particularly hydrocarbyl
groups. Examples of such hydrocarbyl groups are alkyl, particularly
lower alkyl, phenyl, and C.sub.2 -C.sub.5 alkylene groups such as
dimethylene, trimethylene and the like, in which case the compounds
have a spiro structure. The carbocyclic ring may be saturated or
unsaturated, containing an olefinic bond linking the 4- and
5-carbon atoms.
Acylated heterocyclic 1,3-dicarbonyl herbicide compounds of this
invention have the general formula ##STR6## in which R is as
defined herein and Z is a chain which contains 2 or 3 ring atoms,
at least one of which is nitrogen, oxygen or sulfur. Nitrogen atoms
in such rings may be unsubstituted or may be substituted by a
C.sub.1 -C.sub.4 alkyl group. Carbon atoms in such rings may be
unsubstituted or may be substituted similarly to those in the
carbocyclic compounds described above. Where possible, heterocyclic
rings may be saturated or unsaturated.
Examples of heterocyclic 1,3-dicarbonyl structures include, for
instance, barbituric acid derivatives, hydroxypyrones,
3,5-dioxotetrahydropyrans and -thiopyrans, cyclical oxolactones,
cyclical oxothiolactones and oxalactams.
One particular class of herbicide compounds is that in which the
dicarbonyl compound is an optionally sustituted cyclohexanedione
and the acylating group is a substituted benzoyl moiety. That is, R
in Formula B above is substituted phenyl. In general, these
compounds have the formula ##STR7## in which R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are independently hydrogen or
C.sub.1 -C.sub.4 alkyl or
R.sup.1 or R.sup.3 is ##STR8##
in which
R.sub.a is C.sub.1 -C.sub.4 alkyl; phenyl, optionally substituted
by from 2 to 5 methyl groups; or R.sup.3 is hydroxyl and R.sup.1,
R.sup.2, R.sup.4, R.sup.5 and R.sup.6 are independently hydrogen or
C.sub.1 -C.sub.4 alkyl;
or in which R.sup.1 and R.sup.2, or R.sup.3 and R.sup.4, taken
together are C.sub.2 -C.sub.5 alkylene (such compounds have a spiro
structure);
R.sup.7 is halogen (chlorine, bromine, iodine or fluorine); cyano;
C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 haloalkyl; R.sub.k
SO.sub.n in which R.sub.k is C.sub.1 -C.sub.4 alkyl and n=0, 1 or
2; C.sub.1 -C.sub.4 alkoxy; or nitro;
R.sup.8, R.sup.9 and R.sup.10 independently are hydrogen or
substituents including halogen; C.sub.1 -C.sub.4 alkyl; C.sub.1
-C.sub.4 alkoxy, trifluoromethoxy; cyano; nitro; C.sub.1 -C.sub.4
haloalkyl; C.sub.1 -C.sub.4 alkylthio; phenoxy; or substituted
phenoxy in which the substituent is halogen or halomethyl or
both;
R.sub.b S(O)n in which n is 0, 1 or 2; and R.sub.b is C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, phenyl or benzyl,
##STR9## in which R.sub.c is C.sub.1 -C.sub.4 alkyl, --NR.sub.d
R.sub.e in which R.sub.d and R.sub.e independently are hydrogen or
C.sub.1 -C.sub.4 alkyl;
R.sub.f C(O)-- in which R.sub.f is hydrogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl or C.sub.1 -C.sub.4 alkoxy;
SO.sub.2 NR.sub.g R.sub.h in which R.sub.g and R.sub.h
independently are hydrogen or C.sub.1 -C.sub.4 alkyl;
or R.sup.8 and R.sup.9 taken together form a ring structure with
two adjacent carbon atoms of the phenyl ring to which they are
attached.
Compounds of this type, with various substituents on either or both
of the cyclohexane or phenyl rings are disclosed in: European
Patent Application, Publication No. 90262; the following copending
United States patent applications, assigned to the Assignee
herewith, and entitled "Certain 2-(2-Substituted
Benzoyl)-1,3-Cyclohexanediones", Ser. No. 634,408, filed July 31,
1984; Ser. No. 640,791, filed Aug. 17, 1984; Ser. No. 752,702,
filed July 8, 1985; and Ser. No. 722,593, filed Sept. 5, 1985; the
following U.S. patent applications assigned to the Assignee hereof,
Ser. No. 683,900, filed Dec. 20, 1984 and Ser. No. 802,135, filed
Nov. 29, 1985, entitled "Certain
2-(2-Nitrobenzoyl)-1,3-Cyclohexanediones"; Ser. No. 683,899, filed
Dec. 20, 1984, entitled "Certain
2-(2'-Cyanobenzoyl)-1,3-Cyclohexanediones"; Ser. No. 683,898, filed
Dec. 20, 1984 and Ser. No. 802,133, filed Nov. 29, 1985, entitled
"Certain 2-(2'-Substituted Benzoyl)- 1,3-Cyclohexanediones"; Ser.
No. 683,884, filed Dec. 20, 1984 and Ser. No. 802,134, filed Nov.
29, 1985, entitled "Certain
2-(2'-Alkylbenzoyl)-1,3-Cyclohexanediones" (all these patent
applications relating to compounds which are herbicidal): and
Japanese Patent Applications (Publication Nos.) 51/13750 and
51/13755 of Nippon Soda K. K., which disclose some compounds of
this type as intermediates for herbicides. The disclosures of these
documents are hereby incorporated herein.
Some specific types of such acylated heterocyclic 1,3-dicarbonyl
herbicide compounds include:
barbituric acid derivatives such as those of the formula IV
##STR10## in which R.sup.18 and R.sup.19 are hydrogen or C.sub.1
-C.sub.4 alkyl and R is substituted phenyl such as ##STR11## in
which R.sup.15, R.sup.16 and R.sup.17 are as defined hereinafter.
Such compounds are described, for instance, in copending, commonly
assigned United States patent application no. 872,068, filed June
9, 1986; entitled "Certain S-(2-Substituted Benzoyl)-Barbituric
Acids, the disclosure of which is hereby incorporated herein;
oxolactams such as those having the formula V ##STR12## in which
R.sup.11 -R.sup.14 and R.sup.20 are independently hydrogen or
C.sub.1 -C.sub.4 alkyl, or R.sup.11 and R.sup.12 together are
C.sub.2 -C.sub.5 alkylene, t is 0 or 1 and R is substituted phenyl
such as ##STR13## in which R.sup.15 is hydrogen; halogen; C.sub.1
-C.sub.2 alkyl; C.sub.1 -C.sub.2 alkoxy; nitro; cyano; C.sub.1
-C.sub.2 haloalkyl; or R.sub.m SO.sub.n wherein R.sub.m is C.sub.1
-C.sub.2 alkyl and n is 0, 1 or 2; trifluoromethyl or
difluoromethyl; or trifluoromethoxy or difluoromethoxy. Preferably
R.sup.15 is chlorine, bromine, C.sub.1 -C.sub.2 alkyl, C.sub.1
-C.sub.2 alkoxy, trifluoromethyl, cyano, nitro, C.sub.1 -C.sub.2
alkyl, C.sub.1 -C.sub.2 alkoxy, trifluoromethyl, cyano, nitro,
C.sub.1 -C.sub.2 alkylthio or C.sub.1 -C.sub.2 alkylsulfonyl; and
R.sup.16 and R.sup.17 independently are (1) hydrogen, (2) halogen;
(3) C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5)
trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4
haloalkyl; (9) R.sup.b SO.sub.n -- wherein n is the integer 0, 1 or
2; and R.sup.b is (a) C.sub.1 -C.sub.4 alkyl; (b) C.sub.1 -C.sub.4
alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl.
Such compounds are disclosed, for instance, in copending, commonly
assigned U.S. application no. 871,973, filed June 9, 1986, entitled
"Certain 3-(Benzoyl-4-Oxolactams" the disclosure of which is hereby
incorporated by reference;
Herbicidal oxolactones and oxothiolactones within this invention
such as those having the formula VI ##STR14## in which R.sup.21
-R.sup.24 are independently hydrogen or C.sub.1 -C.sub.4 alkyl; or
R.sub.21 and R.sup.22 together are C.sub.2 -C.sub.5 alkylene; or
R.sup.23 and R.sup.24 together are C.sub.2 -C.sub.5 alkylene; or
R.sup.21 and R.sup.23 together form a bond, and R is substituted
phenyl such as ##STR15## in which R.sup.15 -R.sup.17 are as defined
above; and W is oxygen or sulfur. When R.sup.21 and R.sup.23
together form a bond, the compounds contain an unsaturated
heterocyclic ring. Such compounds are disclosed, for instance, in
copending, commonly assigned U.S. application no. 871,975, filed
June 9, 1986; entitled "Certain 4-Oxo-Benzoyl-Valerolactones and
Thiolactones", the disclosure of which is hereby incorporated
herewith;
dioxotetrahydropyrans and -thiopyrans such as those having the
formula VII ##STR16## in which R.sup.26 -R.sup.29 are independently
hydrogen or C.sub.1 -C.sub.4 alkyl or R.sup.26 and R.sup.27
together are C.sub.2 -C.sub.5 alkylene, or R.sup.28 and R.sup.29
together are C.sub.2 -C.sub.5 alkylene; W.sup.2 is oxygen, sulfur
or sulfonyl and R.sup.30 is substituted phenyl such as ##STR17## in
which R.sup.15 -C.sub.17 are as previously defined. Such compounds
are described, for instance, in copending, commonly assigned U.S.
application no. 872,080, filed Sept. 9, 1986, entitled "Certain
Substituted 4-Benzoyl-3,5-Oxo-tetrahydropyrans and Thiopyrans".
Another embodiment of this invention is an herbicidal composition
comprising a 2-(2-substituted benzoyl)-4-(substituted or
unsubstituted phenyl) cyclohexanedione and an antidote with an
inert carrier therefor. The 1,3-cyclohexanedione moiety is
preferably substituted with groups hereinafter defined. The benzoyl
and cyclohexanedione moieties can be further substituted.
Within the scope of this embodiment are compounds in which R in
Formula B above is a substituted phenyl. In general, these
compounds have the formula VIII: ##STR18## wherein R.sup.140 is
halogen; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2 alkoxy;
trifluoromethoxy; or difluoromethoxy; nitro; cyano; C.sub.1
-C.sub.2 haloalkyl; R.sup.a SO.sub.n -- wherein n is 0 or 2; and
R.sup.a is C.sub.1 -C.sub.2 alkyl; trifluoromethyl or
difluoromethyl. Of particular interest are compounds in which
R.sup.140 is chlorine, bromine, C.sub.1 -C.sub.2 alkyl, C.sub.1
-C.sub.2 alkoxy, trifluoromethyl, cyano, nitro, C.sub.1 -C.sub.2
alkylthio or C.sub.1 -C.sub.2 alkylsulfonyl; more preferably
chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl;
R.sup.131 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.132 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.131 and R.sup.132 together are C.sub.2 -C.sub.5 alkylene;
R.sup.133 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.134 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.133 and R.sup.134 together are C.sub.2 -C.sub.5 alkylene;
R.sup.135, R.sup.136, R.sup.137 and R.sup.138 independently are (1)
hydrogen; (2) chlorine, fluorine or bromine; (3) C.sub.1 -C.sub.4
alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5) trifluoromethoxy; (6)
cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl; (9) R.sup.b
SO.sub.n -- wherein n is the integer 0, 1 or 2; and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein
R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4
alkyl;
(11) R.sup.e C(O)-- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or
C.sub.1 -C.sub.4 alkoxy;
(12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as
defined; or
(13) --N(R.sup.c)C(O)R.sup.d wherein R.sup.e and R.sup.d are as
defined; and
R.sup.139 is hydrogen or C.sub.1 -C.sub.4 alkyl.
Preferably R.sup.135 is in the 3-position and R.sup.135 and
R.sup.137 are hydrogen, chlorine, fluorine, trifluoromethyl, cyano,
C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 thioalkyl; or R.sup.135
and R.sup.137 are hydrogen and R.sup.136 and R.sup.138 are in the
4-position; wherein R.sup.136 and R.sup.138 are halogen, cyano,
trifluoromethyl, or R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1
-C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl.
Compounds of this type are described in copending U.S. Application
Ser. No. 906,462, filed Sept. 12, 1986.
Another embodiment of this invention is an herbicidal composition
comprising an herbicidally active 2-(substituted
benzoyl)-cyclohexanedione-1,3 and the acylating group is a
substituted benzoyl moiety and an antidote with an inert carrier
therefor. The 4- and 6-positions of the cyclohexanedione-1,3 moiety
are preferably substituted with groups hereinafter defined, most
preferably with hydrogen or methyl groups. The substituted benzoyl
and cyclohexanedione-1,3 moieties can be further substituted.
Within the scope of this embodiment are the compounds in which R in
Formula B, above, is substituted phenyl. In general, these
compounds have the formula IX: ##STR19## wherein R.sup.50 is
halogen; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2 alkoxy;
trifluoromethoxy or difluoromethoxy; nitro; cyano; C.sub.1 -C.sub.2
haloalkyl; R.sup.a SO.sub.n -- wherein n is 0 or 2; and R.sup.a is
C.sub.1 -C.sub.2 alkyl; trifluoromethyl; or difluoromethyl;
R.sup.41 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.42 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.41 and R.sup.42 together are C.sub.2 -C.sub.5 alkylene;
R.sup.43 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.44 is hyrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.43 and R.sup.44 together are C.sub.2 -C.sub.5 alkylene;
R.sup.45, R.sup.46, R.sup.47 and R.sup.48 independently are (1)
hydrogen; (2) halogen selected from the group consisting of
chlorine, fluorine or bromine; (3) C.sub.1 -C.sub.4 alkyl; (4)
C.sub.1 -C.sub.4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7)
nitro; (8) C.sub.1 -C.sub.4 haloalkyl; (9) R.sup.b SO.sub.n --
wherein n is the integer 0, 1 or 2; and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein
R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4
alkyl;
(11) R.sup.e C(O)-- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or
C.sub.1 -C.sub.4 alkoxy;
(12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as
defined; or
(13) --N(R.sup.c)C(O)R.sup.d wherein R.sup.e and R.sup.d are as
defined; and
R.sup.49 is hydrogen or C.sub.1 -C.sub.4 alkyl.
Of particular interest are compounds in which R.sup.45 is in the
3-position and R.sup.45 is hydrogen, chlorine, fluorine,
trifluoromethyl, cyano, C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4
thioalkyl; or R.sup.45 is hydrogen; or R.sup.46 is in the
4-position; and R.sup.46 is halogen, cyano, trifluoromethyl, or
R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1 -C.sub.4 alkyl,
preferably methyl or C.sub.1 -C.sub.4 haloalkyl, difluoromethyl or
trifluoromethyl.
Compounds of this type are described in copending U.S. patent
application Ser. No. 906,461, filed Sept. 12, 1986.
Another embodiment of this invention is an herbicidal composition
comprising an herbicidally active 2-(2-substituted
benzoyl)-4-(substituted oxy or substituted
thio)-1,3-cyclohexanedione and an antidote with an inert carrier
therefor. The 5- and 6-positions of the 1,3-cyclohexanedione moiety
are preferably substituted with groups hereinafter defined, most
preferably with hydrogen or methyl groups. The substituted benzoyl
and cyclohexanedione moieties can be further substituted.
Within the scope of this embodiment are compounds having the
following structural formula ##STR20## wherein X is oxy, thio,
sulfinyl or sulfonyl;
R.sup.50 is halogen; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2
alkoxy, preferably methoxy; trifluoromethoxy; difluoromethoxy;
nitro; cyano; C.sub.1 -C.sub.2 haloalkyl; R.sup.a SO.sub.n --
wherein n is 0 or 2, preferably 2 and R.sup.a is C.sub.1 -C.sub.2
alkyl; trifluoromethyl or difluoromethyl. Preferably, R.sup.50 is
chlorine, bromine, C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy,
trifluoromethyl, cyano, nitro, C.sub.1 -C.sub.2 alkylthio or
C.sub.1 -C.sub.2 alkylsulfonyl; more preferably chlorine, nitro,
methyl, trifluoromethyl or methylsulfonyl;
R.sup.51 is hydrogen; C.sub.1 -C.sub.4 alkyl; phenyl; or
substituted phenyl;
R.sup.52 is hydrogen or C.sub.1 -C.sub.4 alkyl; or
R.sup.51 and R.sup.52 together are C.sub.2 -C.sub.5 alkylene;
R.sup.53 is hydrogen; C.sub.1 -C.sub.4 alkyl; phenyl; or
substituted phenyl with the proviso that R.sup.51 and R.sup.53 are
not both phenyl or substituted phenyl;
R.sup.54 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.55 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.56 is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, or
phenyl and
R.sup.57 and R.sup.58 independently are (1) hydrogen; (2) halogen;
(3) C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5)
trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4
haloalkyl; (9) R.sup.b SO.sub.n -- wherein n is the integer 0, 1 or
2; and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein
R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4
alkyl;
(11) R.sup.e C(O)-- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or
C.sub.1 -C.sub.4 alkoxy;
(12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as
defined; or
(13) --N(R.sup.c)C(O)R.sup.d wherein R.sup.c and R.sup.d are as
defined.
Compounds of this type are described in copending U.S. patent
application Ser. No. 919,280, filed Oct. 16, 1986.
Another embodiment of this invention is an herbicidal composition
comprising an herbicidally active 2-(2-substituted
benzoyl)-4-(substituted imino, oximino or
carbonyl)-1,3-cyclohexanedione and an antidote with an inert
carrier therefor. The 5- and 6-positions of the
1,3-cyclohexanedione moiety are substituted with groups hereinafter
defined, preferably with hydrogen or methyl groups. The benzoyl and
imino, oximino or carbonyl moieties can be substituted.
Also embodied within the scope of this invention are novel
compounds having the following structural formula ##STR21## wherein
X is oxygen or NR.sup.69 wherein R.sup.69 is hydrogen, C.sub.1
-C.sub.4 alkyl, or C.sub.1 -C.sub.4 alkoxy;
R.sup.60 is halogen; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2
alkoxy; trifluoromethyl or difluoromethoxy; nitro; cyano; C.sub.1
-C.sub.2 haloalkyl; R.sup.a SO.sub.n -- wherein n is 0 or 2; and
R.sup.a is C.sub.1 -C.sub.2 alkyl; trifluoromethyl; or
difluoromethyl. Preferably, R.sup.60 is chlorine, bromine, C.sub.1
-C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, trifluoromethyl, cyano,
nitro, C.sub.1 -C.sub.2 alkylthio or C.sub.1 -C.sub.2
alkylsulfonyl; more preferably chlorine, nitro, methyl,
trifluoromethyl or methylsulfonyl;
R.sup.61 is hyrogen; C.sub.1 -C.sub.4 alkyl; phenyl; or substituted
phenyl;
R.sup.62 is hydrogen or C.sub.1 -C.sub.4 alkyl; or
R.sup.61 and R.sup.62 together are C.sub.2 -C.sub.5 alkylene;
R.sup.63 is hydrogen; C.sub.1 -C.sub.4 alkyl; phenyl; or
substituted phenyl, with the proviso that R.sup.61 and R.sup.63 are
not both phenyl or substituted phenyl;
R.sup.64 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.65 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.66 is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4
haloalkyl;
R.sup.67 and R.sup.68 independently are (1) hydrogen; (2) halogen;
(3) C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5)
trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4
haloalkyl, preferably trifluoromethyl; (9) R.sup.b SO.sub.n --
wherein n is the integer 0, 1 or 2, preferably 2; and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein
R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4
alkyl;
(11) R.sup.e C(O)-- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or
C.sub.1 -C.sub.4 alkoxy;
(12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as
defined; or
(13) --N(R.sup.c)C(O)R.sup.d wherein R.sup.c and R.sup.d are as
defined.
Within this embodiment, preferably R.sup.67 is in the 3-position
and R.sup.67 is hydrogen, chlorine, fluorine, trifluoromethyl,
cyano, C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 thioalkyl; and
preferably R.sup.68 is in the 4-position and R.sup.68 is halogen,
cyano, trifluoromethyl, or R.sup.b SO.sub.2 wherein R.sup.b is
C.sub.1 -C.sub.4 alkyl, or C.sub.1 -C.sub.4 haloalkyl, preferably
chloromethyl, difluoromethyl or trifluoromethyl.
Compounds of this type are described in copending U.S. patent
application Ser. No. 919,278, filed Oct. 16, 1986.
Another embodiment of this invention is an herbicidal composition
comprising an herbicidally active 2-(2-substituted
benzoyl)-4-(substituted)-1,3-cyclohexanedione and an antidote with
an inert carrier therefor. The 5- and 6-positions and the
4-position of the 1,3-cyclohexanedione moiety are preferably
substituted with groups hereinafter defined, most preferably with
halogen or methyl groups. The benzoyl moiety can be substituted,
with the groups as hereinafter recited.
Within the scope of this embodiment are compounds having the
following structural formula ##STR22## wherein R.sup.70 is halogen;
C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2 alkoxy; trifluoromethoxy;
difluoromethoxy; nitro; cyano; C.sub.1 -C.sub.2 haloalkyl; R.sup.a
SO.sub.n -- wherein n is 0 or 2; and R.sup.a is C.sub.1 -C.sub.2
alkyl; trifluoromethyl or difluoromethyl. Preferably, R.sup.70 is
chlorine, bromine, C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy,
trifluoromethyl, cyano, nitro, C.sub.1 -C.sub.2 alkylthio or
C.sub.1 -C.sub.2 alkylsulfonyl; more preferably chlorine, nitro,
methyl, trifluoromethyl or methylsulfonyl;
R.sup.71 is hydrogen; C.sub.1 -C.sub.4 alkyl; halogen; phenyl; or
substituted phenyl;
R.sup.72 is hydrogen or C.sub.1 -C.sub.4 alkyl; or
R.sup.71 and R.sup.72 together are C.sub.2 -C.sub.5 alkylene;
R.sup.73 is hydrogen; C.sub.1 -C.sub.4 alkyl; phenyl; or
substituted phenyl, with the proviso that R.sup.71 and R.sup.73 are
not both phenyl or substituted phenyl;
R.sup.74 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.75 is hydrogen, halogen or C.sub.1 -C.sub.4 alkyl;
R.sup.76 is halogen, nitro, cyano, trifluoromethyl;
--C(O)NR.sub.2.sup.b wherein R.sup.b is hydrogen or C.sub.1
-C.sub.2 alkyl; and
R.sup.77 and R.sup.78 independently are (1) hydrogen; (2) halogen;
(3) C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5)
trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4
haloalkyl; (9) R.sup.b SO.sub.n -- wherein n is the integer 0, 1 or
2; and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein
R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4
alkyl;
(11) R.sup.e C(O)-- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or
C.sub.1 -C.sub.4 alkoxy;
(12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as
defined; or
(13) --N(R.sup.c)C(O)R.sup.d wherein R.sup.c and R.sup.d are as
defined.
Within this embodiment, preferably R.sup.77 is in the 3-position
and R.sup.77 is hydrogen, chlorine, fluorine, trifluoromethyl,
cyano, C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 thioalkyl;
preferably R.sup.78 is in the 4-position and R.sup.78 is halogen,
cyano, trifluoromethyl, or R.sup.b SO.sub.2 wherein R.sup.b is
C.sub.1 -C.sub.4 alkyl, or C.sub.1 -C.sub.4 haloalkyl, preferably
chloromethyl, difluoromethyl or trifluoromethyl.
Compounds of this type are described in copending U.S. patent
application Ser. No. 919,277, filed Oct. 16, 1986.
The term "C.sub.1 -C.sub.4 alkyl" includes methyl, ethyl, n-propyl,
isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term
"halogen" includes chlorine, bromine, iodine and fluorine. The
terms "C.sub.1 -C.sub.4 alkoxy" includes methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and
t-butoxy. The term "C.sub.1 -C.sub.4 haloalkyl" includes the alkyl
groups defined above under C.sub.1 -C.sub.4 alkyl in which one or
more hydrogens is replaced by chlorine, bromine, iodine or
fluorine.
Salts of the above-described compounds are included within the
scope of the instant invention.
One method for production of acylated dicarbonyl compounds is
disclosed in European Patent Application, Publication No. 90262 and
involves the reaction of an optionally substituted
1,3-cyclohexanedione with a substituted benzoyl cyanide. The
reaction is carried out in the presence of zinc chloride and
triethylamine.
The following is a list of sample compounds as found in the above
description of active herbicides.
__________________________________________________________________________
##STR23## Cmpd. No. R3 R.sup.4 R.sup.7 R.sup.8 R.sup.9 R.sup.10
__________________________________________________________________________
51A H H Cl H 4-CH.sub.3 SO.sub.2 H 55A CH.sub.3 CH.sub.3 Cl H
4-CH.sub.3 SO.sub.2 H 90A H H Cl 3-C.sub.2 H.sub.5 O 4-C.sub.2
H.sub.5 SO.sub.2 H
__________________________________________________________________________
##STR24## Comp. No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6
R.sup.8 R.sup.9
__________________________________________________________________________
1C CH.sub.3 CH.sub.3 H H H H H H
__________________________________________________________________________
##STR25## Comp. No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6
R.sup.8 R.sup.9
__________________________________________________________________________
4D CH.sub.3 CH.sub.3 H H H H H H 8D H H H H H H H CF.sub.3 24D
CH.sub.3 CH.sub.3 H H H H H SO.sub.2 CH.sub.3 70D H H H H CH.sub.3
CH.sub.3 H SO.sub.2 CH.sub.2 Cl 71D CH.sub.3 CH.sub.3 OH H CH.sub.3
CH.sub.3 H CF.sub.3
__________________________________________________________________________
##STR26## Comp. No. n R.sup.K R.sup.1 R.sup.2 R.sup.3 R.sup.4
R.sup.5 R.sup.6 R.sup.8 R.sup.9
__________________________________________________________________________
4E 2 CH.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H H H 16E 0 CH.sub.3 H
H H H H H H SO.sub.2 n-C.sub.3 H.sub.7
__________________________________________________________________________
##STR27## Comp. No. R.sup.50 R.sup.51 R.sup.52 R.sup.53 R.sup.54
R.sup. 55 R.sup.56 R.sup.57 R.sup.58
__________________________________________________________________________
8F CH.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H H CH.sub.3 SO.sub.2
29F CF.sub.3 H H H H H H H C.sub.2 H.sub.5 S 36F CH.sub.3 H H H H H
H 3-Cl C.sub.2 H.sub.5 SO.sub.2 50F CF.sub.3 CH.sub.3 CH.sub.3 H H
H H H CF.sub.3
__________________________________________________________________________
##STR28## Cmpd. No. R.sup.140 R.sup.131 R.sup.132 R.sup.133
R.sup.134 R.sup.135 R.sup.136 R.sup.137 R.sup.138 R.sup.139
__________________________________________________________________________
VIII-14 Cl H H Me H H 4-SO.sub.2 Me 2-F H H VIII-17 NO.sub.2 H H H
H H 4-Cl 2-F H Me VIII-24 Cl H H H H H 4-SO.sub.2 Me H H H
__________________________________________________________________________
##STR29## Comp. No. R.sup.50 R.sup.41 R.sup.42 R.sup.43 R.sup.44
R.sup.45 R.sup.46 R.sup.47 R.sup.48 R.sup.49
__________________________________________________________________________
II-4 Cl CH.sub.3 CH.sub.3 H H H 4-SO.sub.2 CH.sub.3 H H H II-6
NO.sub.2 H H H H H 4-Cl H H H
__________________________________________________________________________
##STR30## Cmpd. No. R.sup.15 R.sup.26 R.sup.27 R.sup.28 R.sup.29
R.sup.16 R.sup.17 W.sup.2
__________________________________________________________________________
VII-1 NO.sub.2 CH.sub.3 CH.sub.3 H H H 4-Cl O VII-5 Cl H H H H H
4-Cl S VII-7 Cl CH.sub.3 H CH.sub.3 H H 4-Cl S
__________________________________________________________________________
##STR31## Comp. No. R.sup.15 R.sup.21 R.sup.22 R.sup.23 R.sup.24
R.sup.16 R.sup.17 W
__________________________________________________________________________
VI-1 Cl H CH.sub.3 bond H 4-Cl O VI-4 NO.sub.2 H CH.sub.3 H H H H O
VI-9 NO.sub.2 H CH.sub.3 H CH.sub.3 H 4-Cl O VI-21 Cl H CH.sub.3 H
CH.sub.3 H 4-SO.sub.2 CH.sub.3 S
__________________________________________________________________________
##STR32## Cmpd. No. R.sup.15 R.sup.18 R.sup.19 R.sup.16 R.sup.17
__________________________________________________________________________
IV-1 Cl CH.sub.3 CH.sub.3 H 4-Cl IV-6 NO.sub.2 CH.sub.3 CH.sub.3 H
H IV-13 Cl CH.sub.3 CH.sub.3 3-n-C.sub.3 H.sub.7 4-SO.sub.2 C.sub.2
H.sub.5
__________________________________________________________________________
##STR33## Comp. No. R.sup.15 R.sup.11 R.sup.12 R.sup.13 R.sup.14
R.sup.16 R.sup.17 R.sup.20 t
__________________________________________________________________________
V-1 NO.sub.2 H H H H H 4-Cl n-C.sub.3 H.sub.7 1 V-2 NO.sub.2 H H
n/a n/a H 4-Cl n-C.sub.3 H.sub.7 0 V-3 Cl H H H H H 4-SO.sub.2
CH.sub.3 n-C.sub.3 H.sub.7 1 V-7 NO.sub.2 H H CH.sub.3 CH.sub.3 H
4-Cl CH.sub.3 1 V-15 NO.sub.2 CH.sub.3 H H H H 4-SO.sub.2 CH.sub.3
C.sub.2 H.sub.5 1
__________________________________________________________________________
##STR34##
Comp. No. R.sup.59 R.sup.51 R.sup.52 R.sup.53 R.sup.54 R.sup.55 X
R.sup.56 R.sup.57 R.sup.58
__________________________________________________________________________
X-5 Cl H H H H H S CH.sub.3 H 4-SO.sub.2 CH.sub.3 X-6 NO.sub.2 H H
H H H SO.sub.2 CH.sub.3 H 4-Cl X-13 NO.sub.2 H H H H CH.sub.3 S
CH.sub.3 H H
__________________________________________________________________________
##STR35## Cmpd. No. R.sup.60 R.sup.61 R.sup.62 R.sup.63 R.sup.64
R.sup.65 R.sup.66 R.sup.67 R.sup.68 X
__________________________________________________________________________
XI-1 Cl H H H H H CH.sub.3 H 4-SO.sub.2 CH.sub.3 C.sub.2 H.sub.5ON
XI-6 Cl H H H H H CH.sub.3 3-Cl 4-SO.sub.2 C.sub.2 H.sub.5
CH.sub.3ON XI-7 NO.sub.2 H H H H H CH.sub.3 H 4-Cl CH.sub.3ON XI-8
Cl H H H H H CF.sub.3 H 4-Cl CH.sub.3ON
__________________________________________________________________________
##STR36## Cmpd. No. R.sup.70 R.sup.71 R.sup.72 R.sup.73 R.sup.74
R.sup.75 R.sup.76 R.sup.77 R.sup.78
__________________________________________________________________________
XII-1 Cl H H H H H Br H 4-SO.sub.2 CH.sub.3 XII-6 NO.sub.2 CH.sub.3
CH.sub.3 H H H Br H H XII-7 Cl H H H H H Cl H 4-Cl XII-9 NO.sub.2 H
H CH.sub.3 CH H F H 4-CF.sub. 3
__________________________________________________________________________
DESCRIPTION OF ANTIDOTES
This invention embodies a two-part herbicidal system comprised of
(a) the herbicide as described hereinabove and (b) an effective
antidote therefor. It has been found that such antidote compounds
can be selected from a wide range of chemical substances that have
been found to be effective as herbicide antidotes for the
above-described acylated 1,3-dicarbonyl herbicides. The preferred
compositions of this invention may include any one or more of such
antidotes with the herbicides. The variety of crops on which the
above-described heribicides is useful can be significantly
broadened by the use of an antidote to protect one or more crops
from injury therefrom and render the composition more selective
against weeds. Some of the more important types of antidotes are
amides of haloalkanoic acids, aromatic oxime derivatives, thiazole
carboxylic acids and derivatives, and 1,8-naphthalic anhydride.
Amides of haloalkanoic acids have the generalized formula ##STR37##
in which R is mono- or poly-haloalkyl group. The halogens may be
variously chloro, bromo or iodo; chloro and bromo are the preferred
halogens, and the preferred group for R in these compounds in
dichloromethyl, Cl.sub.2 CH--, i.e., the compounds are amides of
dichloroacetic acid and amides of dibromopropionic acid. In such
compounds the nitrogen is further substituted by at least one other
functional group. This class of compounds also includes those in
which the nitrogen forms a portion of a heterocyclic ring with
substituents, as will be described below.
Antidotes of this type are described in a number of publications
such as U.S. Pat. Nos. 4,021,224; 4,256,481; and 4,294,764, and
British Patent 1,521,540. U.S. Pat. No. 4,021,224 contains a broad
disclosure of such types of compounds and indicates a great many
possibilities for mono- or di-substitution on the nitrogen
atom.
Such useful antidotes include amides of haloalkanoic acids having
the formula ##STR38## in which n is 1 or 2, Y is chlorine or
bromine and R.sup.8 ' and R.sup.9 ' are independently C.sub.1
-C.sub.12 alkyl, C.sub.2 -C.sub.12 alkenyl, C.sub.1 -C.sub.4
alkylene substituted with phenyl; dialkoxyalkyl wherein the alkoxy
and alkyl groups each have 1-4 carbon atoms and R.sup.8 ' and
R.sup.9 ' taken together are C.sub.1 -C.sub.4 alkyleneoxyalkylene,
or alkylenethioalkylene substituted with a spiro 5- to 6-membered
heterocyclic ring, phenyl, alkyl, alkoxyalkyl, or
alkylthioalkyl.
Preferable embodiments of said antidotes include those wherein n is
1 or 2, R.sup.8 ' and R.sup.9 ' are independently C.sub.1 -C.sub.6
alkyl, C.sub.2 -C.sub.6 alkenyl, dialkoxyethyl, cyclic acetal or
C.sub.1 -C.sub.2 alkylene substituted with phenyl. Further
embodiments include those antidotes wherein n is 2, and R.sup.8 '
and R.sup.9 ' are independently C.sub.1 -C.sub.4 alkyl, C.sub.2
-C.sub.4 alkenyl, dimethyoxyethyl, dioxolanylmethyl or benzyl.
One type of antidote disclosed in U.S. Pat. No. 4,021,224 is
N,N-diallyl dichloroacetamide, ##STR39##
It is generally known commercially as R-25788 and is included as an
antidote in several commercial products containing thiolcarbamate
herbicides.
Another class of amides of haloalkanoic acids is that in which the
nitrogen atom is contained in an oxazolidine or thiazolidine ring.
Preferably R is dichloromethyl, and these oxazolidines and
thiazolidines have the general formula ##STR40## wherein R.sup.80,
R.sup.81, R.sup.82, R.sup.83, R.sup.84 and R.sup.85 are
independently hydrogen, lower alkyl, alkoxyalkyl, alkylthioalkyl,
lower alkylsulfonylmethyl or -phenyl, or R.sup.80 and R.sup.81
taken together form an alkylene group, preferably a butylene,
pentylene or hexylene group optionally substituted by one or two
methyl groups and X is oxygen or sulfur. Compounds of these types
are disclosed in a number of patents, including U.S. Pat. Nos.
4,021,224 and 4,256,481. Representative compounds of this type
include (where not specifically mentioned the radical is
hydrogen):
2-2-dimethyl-N-dichloroacetyl oxazolidine (R.sup.80 and R.sup.81
=methyl) (known as 7);
2,2,5-trimethyl-N-dichloroacetyl oxazolidine (R.sup.80, R.sup.81
and R.sup.82 =methyl) (known as 2);
2,2-dimethyl-5-n-propyl-N-dichloroacetyl oxazolidine (R.sup.80,
R.sup.81 =methyl, R.sup.82 =n-propyl);
2,2-dimethyl-5-phenyl-N-dichloroacetyl oxazolidine (R.sup.80,
R.sup.81 =methyl, R.sup.82 =phenyl) (known as 3);
2,2-spirocyclohexyl-N-dichloroacetyl oxazolidine (R.sup.80 plus
R.sup.81 taken together=pentamethylene); and
2,2-dimethyl-N-dichloroacetyl-5-ethyl oxazolidine (R.sup.80,
R.sup.81 =methyl, R.sup.82 =ethyl).
Other compounds in which R.sup.80 and R.sup.81 taken together are
alkylene are disclosed for instance in British Patents 1,512,540
and 2,023,582 and Hungarian Patent 181,621.
A third type of haloalkanoic acid amide is disclosed generally in
U.S. Pat. No. 4,294,764 and has the general formula ##STR41## in
which R.sup.86 may be one of a number of alkyl, alkenyl or alkynyl
moieties; R.sup.87, R.sup.88, R.sup.89 and R.sup.90 are
independently hydrogen or methyl; and n is 0 or 1. A representative
compound of this type is the compound
N-(1,3-dioxolan-2-yl-methyl)-N-(2-propenyl)-2,2-dichloroacetamide,
which has the formula ##STR42## This corresponds to the previous
formula (3) in which R.sup.86 is 2-propenyl, R.sup.87 and R.sup.88
are both hydrogen and n is 0.
Oxime derivatives which are suitable for use as antidotes with
herbicides are disclosed, for instance in U.S. Pat. Nos. 4,070,389
and 4,269,775 and have the general formula ##STR43## in which Ar is
a phenyl or substituted phenyl radical where the substituents are
optionally methyl, methoxy, chlorine, cyano or trifluoromethyl, or
Ar is a naphthyl radical; R.sup.91 is cyano, ##STR44## or
--CN(R.sub.g)(R.sub.h), where R.sub.a and R.sub.b are independently
lower alkyl or together with the carbon form an oxygen or sulfur
containing 5 or 6 membered heterocyclic ring which is unsubstituted
or substituted by lower alkyl, halogen and/or nitro; (R.sub.c) and
(R.sub.d) are independently hydrogen, lower alkyl, cycloalkyl,
which are unsubsituted or further substituted with one or more
halogen, lower alkoxy and/or cyano; (R.sub.g) and (R.sub.h)
together with the nitrogen form a 5 to 6-membered ring which is
unsubstituted or mono- or polysubstituted by halogen, cyano and/or
lower alkyl and which can be interrupted by a nitrogen, oxygen or
sulfur atom. Representative compounds of this type are those in
which R.sup.91 is cyano, and in which R.sup.91 is
1,3-dioxolan-2-yl. The latter compound has the chemical name
O-[2-(1,3-dioxolanyl)methyl]-alpha-cyanobenzaldoxime.
Thiazole carboxylic acids and derivatives suitable for use as
antidotes are disclosed generally in U.S. Pat. No. 4,199,506, and
have the general formula ##STR45## in which R.sup.92 is alkyl,
haloalkyl or trialkoxymethyl; R.sup.93 is variously hydrogen,
agriculturally acceptable cations or various hydrocarbyl or
substituted hydrocarbyl moieties; m is 0 or 1; and R.sup.94 is
chloro, bromo, iodo, lower alkoxy or substituted or unsubstituted
phenoxy. A representative member of this class is the compouund
benzyl-2-chloro-4-trifluoromethyl-5thiazole carboxylate (R.sup.92
=trifluoromethyl; R.sup.93 =benzyl, R.sup.94 =chloro; m=1).
Another useful herbicide antidote compound is disclosed in European
Patent No. 0104495 as having the formula ##STR46## wherein R.sup.95
represents the group ##STR47## in which R.sup.98 a C.sub.1 -C.sub.3
haloalkyl containing from 1 to 3 halogen atoms or a phenyl group
optionally substituted; R.sup.96 represents a hydrogen atom, a
methyl or a phenyl; R.sup.97 represents a C.sub.1 -C.sub.8 alkyl
group, a C.sub.5 -C.sub.6 cycloalkyl group, a cyclohexylmethyl
group, a phenyl group optionally substituted, a benzyl group
optionally substituted, an allyl or propargyl group; and n is zero
or one.
A still further useful antidote is 1,8-naphthalic anhydride.
A representative antidote of that group would be: ##STR48##
The amount of a given antidote to be utilized in combination with
the herbicide composition of this invention and the manner of its
utilization and resulting efficacy can vary according to various
parameters, such as the particular antidote to be employed, the
crop which is to be protected, the amount or rate of herbicide to
be applied, the soil and climatic conditions of the agricultural
environment in which the mixture is to be applied. The selection of
a specific antidote for use in the berbicide composition, the
manner in which it is to be applied (e.g., tank mix, in-furrow
application, seed treatment, etc.), the determination of activity
which is non-phytotoxic but antidotally effective, and the amount
necessary to provide this result, can be readily performed
utilizing the test procedures in the cited patents, such as U.S.
Pat. No. 4,021,224, in accordance with common practice in the
art.
For other descriptions of antidotes and methods of their use,
reference is made to U.S. Pat. No. 3,959,304, Teach, May 25, 1976;
U.S. Pat. No. 3,989,503, Pallos et al., Nov. 2, 1976; U.S. No.
3,131,509, Hoffman, May 5, 1964; U.S. Pat. No. 3,564,768, Hoffman,
Feb. 3, 1971; U.S. Pat. No. 4,137,070, Pallos et al., Jan. 30,
1979; U.S. Pat. No. 4,294,764, Rinehart, Oct. 13, 1981; U.S. Pat.
No. 4,256,481, Gardi et al., May 17, 1981; U.S. Pat. No. 4,415,353,
Pallos et al., Nov. 15, 1983; and U.S. Pat. No. 4,415,352, Pallos
et al., Nov. 15, 1983.
The antidote is applied in conjunction with the herbicide in a
non-phytotoxic antidotally effective amount. By "non-phytotoxic" is
meant an amount of the antidote which causes at most minor or no
injury to the desired crop species. By "antidotally effective" is
meant an antidote used in an amount which is effective as an
antidote with the herbicide to decrease the extent of injury caused
by the herbicide to the desired crop species. The preferred weight
ratio of herbicide to antidote is from about 0.1:1 to about 30:1.
Another preferred weight ratio range is from about 1:1 to about
20:1. An even more preferred weight ratio range is from about 2:1
to about 15:1.
The following examples are for illustrative purposes only and are
not intended as necessarily representative of the overall testing
performed and are not intended to limit the invention in any way.
As one skilled in the art is aware, in herbicidal testing, a
significant number of factors that are not readily controllable can
affect the results of individual tests and render them
non-reproducible. For example, the results may vary depending on
environmental factors, such as amount of sunlight and water, soil
type, pH of the soil, temperature, and humidity, among other
factors. Also, the depth of planting, the application rate of the
herbicide, the application rate of the antidote, and the ratio of
the herbicide-to-antidote application, as well as the nature of
crops being tested, can affect the results of the test. Results may
vary from crop to crop and within the crop varieties.
ANTIDOTES:
The following antidotes were employed in Examples I, II and III and
in Tables I, II, III and IV.
______________________________________ 1 = N,N-diallyl
dichloroacetamide 2 = 2,2,5-trimethyl-N-dichloroacetyl oxazolidine
3 = 2,2-dimethyl-5-n-propyl-N-dichloroacetyl oxazolidine I =
.alpha.-(thiono methoxyamino)-benzacetonitrile II =
O-(2-(1,3-dioxalyl)-methyl) .alpha.-cyano benzaldoxime SC =
2-chloro-4-(trifluoromethyl)-5-thiazole carboxylic acid benzyl
ester 1291 = N-allyl-N-(2-(1,3-dioxalanyl)methyl dichloroacetamide
RR = 2-chloro-N-isopropyl acetanilide 124 = parachlorophenyl
N-methyl carbamate CDAA = 2-chloro-N,N-di-2-propenyl acetamide TCA
= trichloroacetic acid 4 = 2,2-spirocyclohexyl-N-dichloroacetyl
oxazolidine NA = naphthalic anhydride
______________________________________
EXAMPLE I
In a post-emergence application the following compositions were
applied on 2-leaf corn compound No. 24D at 0.125 lb/A on a tank mix
with antidote No. 2 at 0.125.+-.0.15 lb/A. Corn injury with
Compound No. 24D was 60-75% chlorosis and 20% stunting. The
combination with No. 2 resulted in 12-20% chlorosis and 2%
stunting. Also included in this test was Compound No. 8D alone at
0.75 lb/A and in a tank mix with the antidote 2 at 0.75.+-.0.25
lb/A. Corn injury at 0.75 lb/A was 10-18% chlorosis, and 2%
stunting; with No. 2, chlorosis was 2% and no stunting.
EXAMPLE II
This was a field test plot. The logarithmic spray methodology was
employed, calibrated to deliver five half-lives in a strip 6.7 feet
by 95 feet in dimension. This test was performed in a field plot
environment. From the start to the end of the spray run, the rate
of 8D and 8F was held constant at 2 lb ai/A; likewise Cmpd. 24D at
0.125 lb ai/A. For each compound, 2 was sprayed from initial rate
of 0.5 lb/A to a final rate of 0.032 lg/A although 0.032 was the
final rate recorded at the end of the spray run. In the table below
the decrease in intensity of bleaching injury recorded in corn
indicates that 8D, 8F and 24D are responsive to the antidote 2.
______________________________________ Crop: Corn Weeds: Natural
infestation and seeded green foxtail Degree of Bleaching Antidote
Herbicide 2 24D 8F 8D (lb/A) (0.125 lb/A) (2 lb/A) (2 lb/A)
______________________________________ 0.500 0 10 5 0.250 0 60 15
0.125 5 85 15 0.063 20 93 40 0.032 25 98 60 0.000 43 98 98
______________________________________
The natural weeds and the seeded green foxtail were antidoted
against 24D at the antidote rate within the range of 0.25 to 0.5
lb/A. No weed antidoting was noted for 8F and 8D.
EXAMPLE III
Several compounds were applied pre-emergence surface (PES) alone
and with 2 to evaluate antidoting of corn, sorghum and weeds. The
plots were treated with the technical herbicides and formulated
antidote applied sequentially to avoid tank mix and possible
incompatibility problems, if either should exist. Trial design was
randomized complete block using two replications, and the soil was
a sandy loam with 2.3% organic matter. The front 3/4 of each plot
was planted to one row each of corn (Zea mays), cv. DeKalb XL-6060,
and grain sorghum (Sorghum bicolor), cv. Funk's G-251. Seeded
across the back quarter were johnsongrass (Sorghum halepense),
green foxtail (Setaria viridis), giant foxtail (Setaria faberi),
annual morningglory (Ipomoea purpurea), and sicklepod (Casia). Warm
days and cool nights prevailed during the first two weeks after
application, approximating spring-like conditions. The complete
treatment list and initial corn and weed ratings are presented in
the table below.
Sorghum showed almost total necrosis with all herbicides and no
response to the antidote. Good protection from chlorosis and
stunting resulted in corn with all compounds, although 2 appeared
to contribute to stunting in the 51A and 4D treatments. Stand count
in this field test was not uniform due to bird feeding. However,
this did not influence eealuation of the antidoting effect and
subsequent rating. Some minor weed antidoting occurred.
__________________________________________________________________________
Mean Percent Corn Tolerance and Weed Control 2 Weeks After
Treatment Annual Corn Johnson- Green Giant Morning- Compounds and
Rates Tolerance grass foxtail foxtail glory Sicklepod Formulation
(lb ai/A) 1 2 3 CONT SUPP CONT SUPP CONT SUPP CONT SUPP CONT SUPP
__________________________________________________________________________
51A T 1.50 25 10 8 62 92 100 100 74 88 97 99 50 96 4D T 1.00 16 10
5 84 97 100 100 93 99 41 68 17 85 8D T 1.00 81 40 23 60 95 99 93
100 100 100 100 92 99 24D T 0.25 79 75 35 97 99 100 100 93 99 97 99
50 99 51A T + 2 1.50 + 0.25 7 8 15 63 88 100 100 66 91 100 100 17
96 4D T + 2 1.00 + 0.25 2 3 10 72 96 100 100 95 99 72 90 0 88 8D T
+ 2 1.00 + 0.25 7 5 15 42 91 100 100 100 100 100 100 92 98 24D T +
2 0.25 + 0.25 13 8 13 83 97 100 100 93 98 94 98 9 96 CONTROL 4 5 0
0 0 0 0 0 0 0 0 0 0
__________________________________________________________________________
CONT = Control, SUPP = Suppression. 1 = Incidence of chlorosis 2 =
Severity of chlorosis 3 = Stunting T = Technical Material
EXAMPLE IV
SEED TREATMENT
Various combinations of herbicides and antidote were evaluated for
protection of corn and sorghum against herbicide injury in a PES
trial. Soil type was a sandy loam having 2.3% organic matter.
Herbicide treatments were arranged in a randomized complete block
design with two replications. The front 3/4 of each herbicide plot
was planted to four rows each of corn (zea mays), c.v. DeKalb
XL-6060, and grain sorghum (Sorghum bicolor), cv. Funk's G 251.
These rows consisted of no seed treatment and seed treatments of 1,
2 and 3. Across the back 1/4 of the plots were seeded johnsongrass
(Sorghum halapense), green foxtail (Setaria viridis), giant foxtail
(Setaria faberi), annual morningglory (Ipomoea purpurea), and
sicklepod (Cassia). Favorable weather occurred the first two weeks
after application, consisting of warm days and cool nights.
Treatment combinations and initial corn and weed ratings are given
in the following table.
Sorghum necrosis approached 100% in all treatments. Differences in
corn stands between seed treatments resulted primarily from
non-uniform planting depths from row to row. The herbicide/antidote
combinations appeared to have little effect on corn stand.
Protection against chlorosis varied by herbicide and by
antidote.
Results hereinafter are reported as a fraction as follows:
##EQU1##
__________________________________________________________________________
Mean Percent Corn Tolerance and Weed Control 2 Weeks After
__________________________________________________________________________
Treatment Rates Corn Johnson- Green (lb ai/A + Tolerance grass
foxtail Compounds & Formulation ai/W %) 1 2 CONT SUPP CONT SUPP
__________________________________________________________________________
51A T 1.50 20 18 73 97 100 100 51A T + 1 2E 1.50 + 0.50% 0 0 73/73
97/97 100/100 100/100 51A T + 2 2E 1.50 + 0.25% 0 0 73/73 97/97
100/100 100/100 51A T + 2 2E 1.50 + 0.50% 0 0 73/73 97/97 100/100
100/100 4D T 1.00 18 18 74 98 100 100 4D T + 1 6E 1.00 + 0.50% 0 0
74/74 98/98 100/100 100/100 4D T + 2 2E 1.00 + 0.25% 0 0 74/74
98/98 100/100 100/100 4D T + 3 50/ST* 1.00 + 0.50% 0 0 74/74 98/98
100/100 100/100 8D T 1.00 91 38 47 95 100 100 8D T + 1 6E 1.00 +
0.50% 5 8 47/47 95/95 100/100 100/100 8D T + 2 2E 1.00 + 0.25% 0 0
47/47 95/95 100/100 100/100 8D T + 3 50/ST* 1.00 + 0.50% 0 0 47/47
95/95 100/100 100/100 24D T 0.25 100 75 95 99 99 99 24D T + 1 6E
0.25 + 0.50% 47 25 95/95 99/99 99/99 99/99 24D T + 2 2E 0.25 +
0.25% 0 0 95/95 99/99 99/99 99/99 24D T + 3 50/ST* 0.25 + 0.50% 47
28 95/95 99/99 99/99 99/99 1 6E 0.50% 0 0 0 0 0 0 2 2E 0.25% 0 0 0
0 0 0 3 50/ST 0.50% 0 0 0 0 0 0 CONTROL 1 3 0 0 0 0
__________________________________________________________________________
Annual Rates Giant Morning- (lb ai/A + foxtail glory Sicklepod
Compounds & Formulation ai/W %) CONT CONT SUPP CONT SUPP
__________________________________________________________________________
51A T 1.50 100 100 100 94 95 51A T + 1 2E 1.50 + 0.50% 100/100
100/100 100/100 94/94 100/95 51A T + 2 2E 1.50 + 0.25% 100/100
100/100 100/100 94/94 100/95 51A T + 2 2E 1.50 + 0.50% 100/100
100/100 100/100 94/94 100/95 4D T 1.00 100 22 70 57 85 4D T + 1 6E
1.00 + 0.50% 100/100 22/22 70/70 57/57 85/85 4D T + 2 2E 1.00 +
0.25% 100/100 22/22 70/70 57/57 85/85 4D T + 3 50/ST* 1.00 + 0.50%
100/100 22/22 70/70 57/57 85/85 8D T 1.00 100 100 100 92 99 8D T +
1 6E 1.00 + 0.50% 100/100 100/100 100/100 92/57 99/99 8D T + 2 2E
1.00 + 0.25% 100/100 100/100 100/100 92/57 99/99 8D T + 3 50/ST*
1.00 + 0.50% 100/100 100/100 100/100 92/57 99/99 24D T 0.25 100
93/93 99 79 93 24D T + 1 6E 0.25 + 0.50% 100/100 93/93 99/99 79/79
93/93 24D T + 2 2E 0.25 + 0.25% 100/100 93/93 99/99 79/79 93/93 24D
T + 3 50/ST* 0.25 + 0.50% 100/100 93/93 99/99 79/79 93/93 1 6E
0.50% 0 0 0 0 0 2 2E 0.25% 0 0 0 0 0 3 50/ST 0.50% 0 0 0 0 0
CONTROL 0 0 0 0 0
__________________________________________________________________________
*Seed treatment powdered formulation. CONT = control; SUPP =
suppression. 1 = Incidence of chlorosis. 2 = Severity of chlorosis.
T = Technical Material 2E and 6E represent formulations which
contain 2 and 6 lbs/gal and an emulsifier.
______________________________________ TESTS TABLES I, II, III, IV
______________________________________ Condition of test: Tank Mix
and Seed Treatment Soil Type: Sandy Loam Method of application and
procedure: Pre-emergence surface applied as tank mix (PES-TM); or
Seed treatment 10 grams of seeds treated with antidote Compound at
various weight percents as indicated. Ratings as indicated.
Seedings: Crop: Corn 25A - CN 25A Corn 55A - CN 55A Corn XL-379 -
CN XL-379 Corn XL-67 - CN XL-67 Corn XL-71 - CN XL-71 Corn Funks
G-4315 - CN G-4315 Corn XL-447 - CN XL-447 Corn XL-23A - CN XL-23A
Corn Pioneer 3475 - CN 3475 Corn Sweet - CN Sweet Weed: Yellow
Nutsedge - YNS Green Foxtail - GFT Watergrass - WG Shattercane -
SHC ______________________________________
The herbicide was surface applied preemergence to the planted
treated seed. The emerged plants were rated 3 weeks after
treatment. The plants were compared to plants which had not
received treatments.
TABLE I ______________________________________ PES Tank Mix Rated
26 Days Treatment Rate* Herbicide + Antidote lb/A XL-55 FUNKS WG
______________________________________ 4D + 1 + 2 8/35 38/40 99/95
4D + 1 + 1 10/35 30/40 99/95 2 1 + 2 25/35 25/40 99/95
______________________________________ *Herbicide + Antidote
TABLE II
__________________________________________________________________________
PES Tank Mix Antidote Test Rated 3 weeks Treatment: Herbicide Rate*
CN CN CN CN CN + Antidote lb/A 25A 55A XL-379 YNS G-4315 XL-71
__________________________________________________________________________
4D + 1 + 0.5 3/38 8/65 -- 85/87 18/60 10/60 1 1 + 1 10/38 18/65 --
85/87 25/60 35/60 1 + 2 10/38 15/65 -- 85/87 15/60 0/60 4D + 1 +
0.5 7/38 13/65 -- 85/87 15/60 8/60 2 1 + 1 3/38 10/65 -- 85/87
18/60 10/60 1 + 2 3/38 5/65 -- 90/87 10/60 5/60 51A + 1 + 0.5 3/3
0/3 25/15 90/90 3/10 5/13 1 1 + 1 0/3 0/3 25/15 90/90 3/10 8/13 1 +
2 0/3 0/3 -- 90/90 5/10 5/13 51A + 1 + 0.5 3/3 0/3 -- 90/90 3/10
8/13 2 1 + 1 0/3 0/3 0/15 90/90 5/10 3/13 1 + 2 0/3 3/3 0/15 90/90
3/10 5/13
__________________________________________________________________________
TABLE III
__________________________________________________________________________
Seed Treatment (10 g seeds/5 mg antidote: 0.05% by w/w) Rated 3
weeks Treatment: Herbicide Rate* CN CN CN CN CN + Antidote lb/A 25A
55A XL-379 YNS G-4315 XL-71
__________________________________________________________________________
4D + 0.5 0/5 0/20 0/40 83/85 40/20 20/15 1 1 20/38 45/65 -- 85/87
60/60 45/60 4D + 0.5 0/5 3/20 5/40 85/85 3/20 0/15 2 1 3/38 0/65 --
87/87 25/60 18/60 51A + 1 5/3 3/3 -- 90/90 40/10 13/13 1 2 20/25
20/50 -- 90/95 65/50 65/28 51A + 1 3/3 0/3 -- 90/90 5/10 3/13 2 2
25/25 0/50 -- 90/95 18/50 15/28
__________________________________________________________________________
*Herbicide + Antidote
TABLE IV
__________________________________________________________________________
PES Tank mix (25 gal/A) Rated 16 days Herb. + Ant. Rate CN CN CN CN
Treatment lb/A GFT XL-55 XL-447 XL-23A 3475
__________________________________________________________________________
4D + 0.5 + 0.5 100/100 5/40 0/35 0/35 0/20 2 0.5 + 1 100/100 0/40
0/35 0/35 0/20 4D + 0.5 + 0.5 100/100 0/40 10/35 10/35 10/20 1 0.5
+ 1 100/100 10/40 10/35 10/35 0/20 0.5 + 2 100/100 0/40 0/35 0/35
0/20 4D + 0.5 + 0.125 100/100 20/40 20/35 40/35 50/20 I 0.5 + 0.25
100/100 40/40 40/35 45/35 45/20 0.5 + 0.5 100/100 40/40 10/35 25/35
40/20 4D + 0.5 + 0.125 100/100 55/40 45/35 50/35 50/20 II 0.5 +
0.25 100/100 60/40 55/35 55/35 60/20 0.5 + 0.5 100/100 30/40 35/35
35/35 30/20 4D + 0.5 + 0.125 100/100 15/40 15/35 30/35 15/20 SC 0.5
+ .25 100/100 45/40 15/35 25/35 25/20 0.5 + 0.5 100/100 35/40 10/35
10/35 20/20 4D + 0.5 + 0.5 100/100 45/40 20/35 30/35 25/20 4 0.5 +
1 100/100 30/40 25/35 25/35 30/20 4D + 0.5 + 0.125 100/100 45/40
30/35 45/35 50/20 124 0.5 + 0.25 100/100 55/40 50/35 50/35 60/20 4D
+ 0.5 + 0.5 100/100 5/40 15/35 30/35 20/20 1292 0.5 + 1 100/100
0/40 0/35 15/35 10/20 4D + 0.5 + 0.125 100/100 55/40 35/35 45/35
45/20 NA 0.5 + 0.25 100/100 45/40 45/35 45/35 40/20 0.5 + 0.5
100/100 25/40 10/35 25/35 15/20 4D + 0.5 + 0.5 100/100 15/40 15/35
0/35 0/20 3 0.5 + 1 100/100 15/40 10/35 0/35 15/20 0.5 + 2 100/100
5/40 0/35 10/35 15/20 4D + 0.5 + 0.125 100/100 25/40 40/35 40/35
50/20 RR 0.5 + 0.25 100/100 55/40 35/35 30/35 35/20 0.5 + 0.5
100/100 45/40 25/35 35/35 40/20 4D + CDAA 0.5 + 0.125 100/100 35/40
40/35 45/35 35/35 0.5 + 0.25 100/100 40/40 40/35 45/35 30/35 0.5 +
0.5 100/100 55/40 55/35 45/35 35/35 4D + TCA 0.5 + 0.125 100/100
60/40 30/35 35/35 30/20 0.5 + 0.25 100/100 60/40 45/35 45/35 35/20
0.5 + 0.5 100/100 50/40 40/35 65/35 60/20
__________________________________________________________________________
TABLE IVA ______________________________________ Application PES
Tank Mix (25 gal/A) Soil Sandy loam Flats 9" .times. 6" .times. 4"
aluminum flats Rated 23 days after treatment Seeding SETVI (green
foxtail), XL-55A corn, XL-23A corn, Pioneer 3475 corn Treat- CN CN
ment Rate (lb/A) SETVI XL-55A XL-23A CN3475
______________________________________ 4D 0.5 100 15 30 45 4D + 0.5
+ 0.5 100/100 5/15 5/30 5/45 2 0.5 + 1.0 100/100 0/15 5/30 5/45 4D
+ 0.5 + 0.5 100/100 10/15 15/30 10/45 1 0.5 + 1.0 100/100 25/15
15/30 0/45 4D + 0.5 + 0.5 100/100 5/15 10/30 20/45 3 0.5 + 1.0
100/100 5/15 5/30 5/45 4D + 0.5 + 0.125 100/100 25/15 30/30 20/45 I
0.5 + 1.0 100/100 15/15 25/25 25/45 4D + 0.5 + 0.125 100/100 20/15
30/30 29/45 II 0.5 + 1.0 100/100 35/15 25/30 25/45 4D + 0.5 + 0.125
100/100 20/15 20/30 25/45 SC 0.5 + 0.25 100/100 5/15 20/30 15/45 4D
+ 0.5 + 0.5 100/100 20/15 15/30 45/45 4 0.5 + 1.0 100/100 20/15
25/30 25/45 4D + 0.5 + 0.125 100/100 30/15 50/30 65/45 124 0.5 +
0.25 100/100 40/15 65/30 70/45 4D + 0.5 + 0.5 100/100 20/15 15/30
0/45 1292 0.5 + 1.0 100/100 15/15 15/30 0/45 4D + 0.5 + 0.5 100/100
60/15 60/30 60/45 NA 0.5 + 1.0 100/100 30/15 25/30 0/45 4D + 0.5 +
0.5 100/100 60/15 60/30 60/45 RR 0.5 + 1.0 100/100 20/15 70/30
80/45 4D + 0.5 + 0.5 100/100 30/15 60/30 45/45 CDAA 0.5 + 1.0
100/100 65/15 60/30 35/45 4D + 0.5 + 0.5 100/100 50/15 60/30 40/45
TCA 0.5 + 1.0 100/100 40/15 25/30 30/45 Con- -- 0 0 0 0 trol 0 0 0
0 ______________________________________
TABLES V, V-A, V-B
MATERIAL AND METHODS
The following herbicide/antidote tests were conducted with various
plant species. The corn hybrids and weed species employed in each
test for Tables V, V-A and V-B are as follows:
AMARE--Amaranthus retroflexus--(redroot pigweed)
SETVI--Setaria viridis--(green foxtail)
ECHCG--Echinochloa crusgalli--(watergrass)
Corn--DeKalb XL64; DeKalb XL-23A; Pioneer 3475.
Herbicide compounds and antidotes employed in the tests were
sprayed in an acetone-water solution containing polyoxyethylene
sorbitan monolaurate emulsifier. Herbicides and antidotes were
applied as preemergence tank mix solution (PES) with a cover volume
of 25 gal/A. All seeds were seeded in aluminum flats
(16.times.23.times.7 cm) of which holes were punched in the bottom
to allow water drainage. Seeds were planted 3 cm deep, except that
AMARE (Amaranthus retroflexus), which was planted 1.5 cm deep, in a
sandy loam soil fortified with fertilizer (17-17-17; Garden Valley
Fertilizer Co., San Jose, CA 95112) and the fungicide Captan 80W.
All compounds were applied preemergence tank mix and all compounds
were applied with linear spray table.
After treatment, all flats were placed into a greenhouse.
Greenhouses were maintained at about 25.degree. C. and 20.degree.
C., day and night temperatures, respectively. All flats were
watered with overhead sprinkling. After treatment visual ratings of
weed control and crop injury were recorded. Ratings were stated as
percentage of control or injury of each individual species as
compared with an untreated control. The injury ratings range from 0
to 100%, where 0 represents no effect on growth and 100 represents
complete kill.
TABLES V, V-A, V-B
The following compounds were employed as examples of antidotes in
Tables V, V-A, and V-B.
______________________________________ 1 N,N-diallyl
dichloroacetamide 5 2,2-bis-(ethylthio)N,N-diallylacetamide 6
2,2-dichloro-N-ethyl-N-benzyl acetamide 7
2,2-dimethyl-3-dichloroacetyl oxazolidine 2
2,2,5-trimethyl-N-dichloroacetyl oxazolidine 8
2-methyl-2-ethyl-N-dichloroacetyl oxazolidine 4
2,2-spirocyclohexyl-N-dichloroacetyl oxazolidine 9
2,2-dimethyl-N-dichloroacetyl thiazolidine 10
2-propyl-3-dichloroacetyl oxazolidine 11
2,5-dimethyl-3-dichloroacetyl oxazolidine 12
2-methyl-2-isopropyl-3-dichloroacetyl oxazolidine 13
N-t-butyl-2,3-dibromopropionamide 14
2,2,4-trimethyl(3-dichloroacetyl)-1,3-oxazolidine 15 N-t-pentyl
2,3-dibromopropionamide 16 2,2,4-trimethyl-3-dichloroacetyl
oxazolidine 17 2,2,5,5-tetramethyl-3-dichloroacetyl oxazolidine 18
2,2-dimethyl-3-dichloroacetyl-5-propyl oxazolidine 19
3-dichloroacetyl-2,2,5-trimethyl thiazolidine 20
2,2,4,5-tetramethyl-3-dichloroacetyl oxazolidine 21
N-(dimethyl-2-butynyl)-2,3-dibromopropionamide 22
2,2-dimethyl-N-dichloroacetyl-5-ethyl oxazolidine 23
2,5-dimethyl-2-ethyl-3-dichloroacetyl oxazolidine 24
2,2-dimethyl-3-dichloroacetyl-5-butyl oxazolidine 25
2,2-dimethyl-3-dichloroacetyl-5-methoxymethyl oxazolidine 26
2,2-dimethyl-3-dichloroacetyl-5-ethoxymethyl oxazolidine 27
2,2-dimethyl-3-dichloroacetyl-4,5-tetramethylene oxazolidine 28
2,2-dimethyl-3-dichloroacetyl-4,5-trimethylene oxazolidine 29
2,2-dimethyl-3-dichloroacetyl-5-ethyl-thiomethyl oxazolidine 30
N-dichloroacetyl-2-trichloromethyl-5-methyl oxazolidine 31
2,2,5-trimethyl-3-hydroxyacetyl oxazolidine 32
2-methyl-2-dichloromethyl-1,3-dioxolane
______________________________________
TABLE V
__________________________________________________________________________
Rate kg/ha Treatment Herb + Ant. AMARE SETVI ECHCG CN 64 CN23A
CN3475
__________________________________________________________________________
RATING 3 WEEKS AFTER TREATMENT 24D + 0.28 + 93/98 100/88 95/100
30/50 45/55 70/58 2 0.07 24D + 0.28 + 100/98 100/88 100/100 33/50
60/55 63/58 2 0.14 24D + 0.28 + 100/98 90/88 100/100 23/50 13/55
43/55 2 0.28 24D + 0.28 + 95/98 98/88 100/100 38/50 48/55 53/58 2
0.56 24D + 0.28 + 95/98 100/88 100/100 78/50 60/55 68/58 7 0.14 24D
+ 0.28 + 100/98 100/88 100/100 35/50 40/55 60/58 7 0.28 24D + 0.28
+ 95/98 100/88 100/100 35/50 28/55 58/58 7 0.56 24D + 0.28 + 100/98
100/88 100/100 25/50 43/55 68/58 9 0.14 24D + 0.28 + 100/98 98/88
100/100 35/50 53/55 63/58 9 0.28 24D + 0.28 + 98/98 95/88 100/100
40/50 35/55 38/58 9 0.56 24D + 0.28 + 100/98 100/88 100/100 50/50
85/55 85/58 6 0.14 24D + 0.28 + 100/98 100/88 100/100 38/50 50/55
53/58 6 0.28 24D + 0.28 + 100/98 100/88 100/100 58/50 50/55 60/58 6
0.56 24D + 0.28 + 100/98 100/88 100/100 35/50 30/55 40/55 4 0.14
24D + 0.28 + 98/98 100/88 100/100 80/50 80/55 70/58 4 0.28 24D +
0.28 + 100/98 100/88 100/100 50/50 60/55 55/58 4 0.56 24D + 0.28 +
100/98 100/88 100/100 83/50 65/55 63/58 1 0.14 24D + 0.28 + 99/98
100/88 100/100 65/50 70/55 53/58 1 0.28 24D + 0.28 + 98/98 95/88
100/100 38/50 50/55 53/58 1 0.56 24D + 0.56 + 100/100 100/100
100/100 70/85 63/88 43/80 2 0.07 24D + 0.56 + 100/100 100/100
100/100 80/85 78/88 70/80 2 0.14 24D + 0.56 + 100/100 100/100
100/100 75/85 78/88 75/80 2 0.28 24D + 0.56 + 98/100 100/100
100/100 63/85 68/88 60/80 2 0.56 24D + 0.56 + 98/100 100/100
100/100 68/85 75/88 65/80 7 0.14 24D + 0.56 + 100/100 100/100
100/100 60/85 80/88 85/80 7 0.28 24D + 0.56 + 100/100 100/100
100/100 58/85 68/88 78/80 7 0.56 24D + 0.56 + 98/100 100/100
100/100 60/85 73/88 78/80 9 0.14 24D + 0.56 + 85/100 95/100 100/100
58/85 75/88 65/80 9 0.28 24D + 0.56 + 98/100 100/100 100/100 65/85
78/88 75/80 9 0.56 24D + 0.56 + 100/100 100/100 100/100 80/85 80/88
78/80 6 0.14 24D + 0.56 + 98/100 100/100 100/100 90/85 88/88 85/80
6 0.28 24D + 0.56 + 100/100 100/100 100/100 85/85 78/88 73/80 6
0.56 24D + 0.56 + 100/100 100/100 100/100 80/85 85/88 83/80 4 0.14
24D + 0.56 + 98/100 100/100 100/100 75/85 70/88 88/80
4 0.28 24D + 0.56 + 100/100 100/100 100/100 98/85 95/88 73/80 4
0.56 24D + 0.56 + 100/100 100/100 100/100 75/85 83/88 75/80 1 0.14
24D + 0.56 + 100/100 100/100 100/100 63/85 90/88 95/80 1 0.28 24D +
0.56 + 100/100 100/100 100/100 68/85 80/88 80/80 1 0.56 4D + 0.56 +
93/97 100/100 100/100 15/15 0/15 13/23 2 0.07 4D + 0.56 + 63/97
100/100 100/100 10/15 15/15 20/23 2 0.14 4D + 0.56 + 78/97 100/100
100/100 20/15 15/15 20/23 2 0.28 4D + 0.56 + 83/97 100/100 100/100
15/15 20/15 20/23 2 0.56 4D + 0.56 + 65/97 100/100 100/100 8/15
10/15 15/23 7 0.14 4D + 0.56 + 83/97 100/100 100/100 25/15 20/15
20/23 7 0.28 4D + 0.56 + 75/97 100/100 100/100 0/15 13/15 8/23 7
0.56 4D + 0.56 + 50/97 98/100 100/100 0/15 8/15 0/23 9 0.14 4D +
0.56 + 35/97 100/100 100/100 0/15 0/15 8/23 9 0.28 4D + 0.56 +
98/97 100/100 100/100 0/15 8/15 5/23 9 0.56 4D + 0.56 + 70/97
100/100 100/100 10/15 8/15 8/23 6 0.14 4D + 0.56 + 75/97 100/100
100/100 3/15 0/15 5/23 6 0.28 4D + 0.56 + 75/97 100/100 100/100
5/15 0/15 5/23 6 0.56 4D + 0.56 + 88/97 100/100 100/100 20/15 5/15
8/23 4 0.14 4D + 0.56 + 75/97 100/100 100/100 13/15 5/15 5/23 4
0.28 4D + 0.56 + 98/97 100/100 100/100 15/15 13/15 15/23 4 0.56 4D
+ 0.56 + 63/97 100/100 100/100 20/15 0/15 8/23 1 0.14 4D + 0.56 +
50/97 100/100 100/100 13/15 5/15 5/23 1 0.28 4D + 0.56 + 78/97
100/100 100/100 5/15 15/15 10/23 1 0.56 4D + 1.12 + 98/65 100/100
100/100 5/13 15/25 8/25 2 0.07 4D + 1.12 + 98/65 100/100 100/100
30/13 13/25 10/25 2 0.14 4D + 1.12 + 85/65 100/100 100/100 5/13
10/25 13/25 2 0.28 4D + 1.12 + 58/65 100/100 100/100 18/13 20/25
13/25 2 0.56 4D + 1.12 + 48/65 100/100 100/100 18/13 15/25 15/25 7
0.14 4D + 1.12 + 100/65 100/100 100/100 18/13 5/25 13/25 7 0.28 4D
+ 1.12 + 60/65 100/100 100/100 23/13 30/25 30/25 7 0.56 4D + 1.12 +
63/65 100/100 100/100 20/13 18/25 18/25 9 0.14 4D + 1.12 + 100/65
100/100 100/100 30/13 15/25 10/25 9 0.28 4D + 1.12 + 65/65 100/100
100/100 10/13 15/25 15/25 9 0.56 4D + 1.12 + 93/65 100/100 100/100
20/13 18/25 20/25 6 0.14 4D + 1.12 + 93/65 100/100 100/100 13/13
20/25 18/25 6 0.28 4D + 1.12 + 58/65 80/100 98/100 8/13 18/25
8/25 6 0.56 4D + 1.12 + 68/65 100/100 100/100 20/13 20/25 45/25 4
0.14 4D + 1.12 + 100/65 100/100 100/100 50/13 28/25 33/25 4 0.28 4D
+ 1.12 + 58/65 100/100 100/100 33/13 35/25 30/25 4 0.56 4D + 1.12 +
58/65 100/100 100/100 30/13 20/25 30/25 1 0.14 4D + 1.12 + 50/65
100/100 100/100 25/13 18/25 18/25 1 0.28 4D + 1.12 + 68/65 100/100
100/100 18/13 15/25 25/25 1 0.56 4D + 0.84 + 48/58 100/100 100/100
25/75 28/80 78/78 22 0.14 4D + 0.84 + 60/58 100/100 100/100 10/75
8/80 23/78 22 0.28 4D + 0.84 + 58/58 100/100 100/100 5/75 8/80
23/78 22 0.56 4D + 0.84 + 58/58 100/100 100/100 18/75 8/80 18/78 22
1.12 4D + 0.84 + 30/58 100/100 100/100 23/75 30/80 30/78 13 0.14 4D
+ 0.84 + 93/58 100/100 100/100 43/75 50/80 60/78 13 0.28 4D + 0.84
+ 50/58 100/100 100/100 15/75 35/80 43/78 13 0.56 4D + 0.84 + 58/58
100/100 100/100 40/75 40/80 50/78 13 1.12 4D + 0.84 + 58/58 100/100
100/100 38/75 43/80 38/78 32 0.14 4D + 0.84 + 25/58 100/100 100/100
75/75 63/80 73/78 32 0.28 4D + 0.84 + 80/58 100/100 100/100 30/75
30/80 35/78 32 0.56 4D + 0.84 + 75/58 100/100 100/100 13/75 30/80
43/78 32 1.12 RATING 20 DAYS AFTER TREATMENT 70D + 0.375 + 75/47
100/95 100/100 50/44 60/49 50/74 2 0.063 70D + 0.375 + 55/47 100/95
100/100 68/44 68/49 99/74 2 0.125 70D + 0.375 + 85/47 100/95
100/100 33/44 40/49 40/74 2 0.25 70D + 0.375 + 45/47 88/95 100/100
58/44 35/49 43/74 7 0.063 70D + 0.375 + 43/47 98/95 100/100 70/44
75/49 70/74 7 0.125 70D + 0.375 + 38/47 100/95 100/100 65/44 58/49
85/74 7 0.25 70D + 0.375 + 38/47 75/95 100/100 25/44 40/49 43/74 9
0.063 70D + 0.375 + 88/47 88/95 100/100 68/44 73/49 88/74 9 0.125
70D + 0.375 + 35/47 100/95 100/100 60/44 65/49 70/74 9 0.25 70D +
0.375 + 30/47 83/95 98/100 25/44 45/49 45/49 18 0.063 70D + 0.375 +
63/47 95/95 100/100 45/44 65/49 70/49 18 0.125 70D + 0.375 + 63/47
85/95 100/100 50/44 73/49 85/49 18 0.25 70D + 0.375 + 43/47 88/95
100/100 38/44 45/49 68/49 25 0.063 70D + 0.375 + 45/47 95/95
100/100 45/44 80/49 90/49 25 0.125 70D + 0.375 + 83/47 95/95
100/100 63/44 60/49 75/49 25 0.25 70D + 0.375 + 25/47
100/100 100/100 60/44 60/49 73/49 29 0.063 70D + 0.375 + 38/47
98/100 100/100 58/44 65/44 83/49 29 0.125 70D + 0.375 + 33/47
88/100 100/100 58/44 73/44 93/49 29 0.25 8D + 0.75 + 99/97 100/100
100/100 20/23 23/28 22/41 2 0.063 8D + 0.75 + 95/97 100/100 100/100
20/23 20/28 20/41 2 0.125 8D + 0.75 + 68/97 100/100 100/100 13/23
15/28 23/41 2 0.25 8D + 0.75 + 83/97 98/100 100/100 28/23 30/28
25/41 7 0.063 8D + 0.75 + 100/97 100/100 100/100 20/23 20/28 18/41
7 0.125 8D + 0.75 + 88/97 100/100 100/100 15/23 10/28 15/41 7 0.25
8D + 0.75 + 95/97 95/100 100/100 3/23 5/28 25/41 9 0.063 8D + 0.75
+ 85/97 100/100 100/100 13/23 18/28 23/41 9 0.125 8D + 0.75 + 88/97
100/100 100/100 5/23 10/28 13/41 9 0.25 8D + 0.75 + 100/97 95/100
100/100 8/23 10/28 33/41 18 0.063 8D + 0.75 + 98/97 100/100 100/100
18/23 45/28 43/41 18 0.125 8D + 0.75 + 88/97
100/100 100/100 28/23 25/28 38/41 18 0.25 8D + 0.75 + 80/97 100/100
100/100 15/23 23/28 28/41 25 0.063 8D + 0.75 + 95/97 100/100
100/100 33/23 38/28 50/41 25 0.125 8D + 0.75 + 98/97 100/100
100/100 58/23 35/28 55/41 25 0.25 8D + 0.75 + 88/97 100/100 100/100
5/23 3/28 13/41 29 0.063 8D + 0.75 + 88/97 85/100 100/100 13/23
13/23 20/41 29 0.125 8D + 0.75 + 100/97 100/100 100/100 8/23 10/23
13/41 29 0.25
__________________________________________________________________________
TABLE V-A
__________________________________________________________________________
Rate lb/A Treatment Herb + Ant. AMARE SETVI ECHCG CN 64 CN23A
CN3475
__________________________________________________________________________
RATING 23 DAYS AFTER TREATMENT 24D + 0.75 + 35/53 95/98 95/100 5/13
5/15 15/18 19 0.063 24D + 0.75 + 75/53 100/98 100/100 40/13 50/15
60/18 19 0.125 24D + 0.75 + 100/53 100/98 100/100 20/13 35/15 40/18
19 0.25 24D + 0.75 + 80/53 100/98 98/100 10/13 10/15 15/18 24 0.063
24D + 0.75 + 75/53 100/98 100/100 40/13 45/15 40/18 24 0.125 24D +
0.75 + 75/53 100/98 100/100 20/13 15/15 35/18 24 0.25 24D + 0.75 +
75/53 100/98 100/100 25/13 25/15 30/18 24 0.5 24D + 0.75 + 80/53
100/98 100/100 5/13 5/15 5/18 11 0.063 24D + 0.75 + 95/53 100/98
100/100 35/13 40/15 35/18 11 0.125 24D + 0.75 + 100/53 100/98
100/100 10/13 15/15 20/18 11 0.25 24D + 0.75 + 100/53 100/98
100/100 20/13 25/15 20/18 11 0.5 24D + 0.75 + 85/53 100/98 100/100
5/13 0/15 5/18 12 0.063 24D + 0.75 + 60/53 100/98 100/100 35/13
25/15 25/18 12 0.125 24D + 0.75 + 98/53 100/98 100/100 10/13 25/15
30/18 12 0.25 24D + 0.75 + 98/53 100/98 100/100 10/13 25/15 20/18
12 0.5 24D + 0.75 + 75/53 100/98 100/100 0/13 0/15 0/18 14 0.063
24D + 0.75 + 100/53 100/98 100/100 35/13 25/15 25/18 14 0.125 24D +
0.75 + 100/53 100/98 100/100 5/13 15/15 20/18 14 0.25 24D + 0.75 +
100/53 100/98 100/100 5/13 35/15 25/18 14 0.5 24D + 0.75 + 75/53
100/98 100/100 10/13 10/15 10/18 16 0.063 24D + 0.75 + 90/53 100/98
100/100 5/13 15/15 25/18 16 0.125 24D + 0.75 + 100/53 100/98
100/100 30/13 35/15 35/18 16 0.25 24D + 0.75 + 70/53 100/98 100/100
35/13 40/15 45/18 16 0.5 24D + 0.75 + 100/53 100/98 100/100 5/13
0/15 10/18 17 0.063 24D + 0.75 + 100/53 100/98 100/100 5/13 10/15
10/18 17 0.125 24D + 0.75 + 100/53 100/98 100/100 60/13 60/15 60/18
17 0.25 24D + 0.75 + 100/53 100/98 100/100 20/13 30/15 35/18 17 0.5
24D + 0.75 + 100/53 100/98 100/100 15/13 25/15 5/18 20 0.063 24D +
0.75 + 90/53 100/98 100/100 30/13 50/15 40/18 20 0.125 24D + 0.75 +
90/53 100/98 100/100 30/13 40/15 40/18 20 0.25 24D + 0.75 + 100/53
100/98 100/100 35/13 40/15 30/18 20 0.5 24D + 0.75 + 75/53 100/98
100/100 5/13 10/15 5/18 23 0.063 24D + 0.75 + 95/53 100/98 100/100
40/13 50/15 40/18 23 0.125 24D + 0.75 + 100/53 100/98 100/100 5/13
15/15 20/18
23 0.25 24D + 0.75 + 90/53 100/98 100/100 5/13 0/15 25/18 23 0.5
RATING 24 DAYS AFTER TREATMENT 4D + 0.75 + 25/100 100/100 100/100
5/40 10/35 5/35 8 0.125 4D + 0.75 + 100/100 100/100 100/100 5/40
5/35 35/35 8 0.25 4D + 0.75 + 100/100 100/100 100/100 10/40 5/35
20/35 8 0.5 4D + 0.75 + 100/100 100/100 100/100 10/40 10/35 10/35 8
1.0 4D + 0.75 + 90/100 100/100 100/100 5/40 5/35 20/35 10 0.125 4D
+ 0.75 + 95/100 100/100 100/100 5/40 10/35 15/35 10 0.25 4D + 0.75
+ 95/100 100/100 100/100 15/40 20/35 40/35 10 0.5 4D + 0.75 +
98/100 100/100 100/100 15/40 15/35 40/35 10 1.0 4D + 0.75 + 98/100
100/100 100/100 5/40 10/35 5/35 30 0.125 4D + 0.75 + 100/100
100/100 100/100 20/40 30/35 40/35 30 0.25 4D + 0.75 + 100/100
100/100 100/100 10/40 10/35 35/35 30 0.5 4D + 0.75 + 100/100
100/100 100/100 15/40 30/35 45/35 30 1.0 4D + 0.75 + 100/100
100/100 100/100 10/40 10/35 10/35 31 0.125 4D + 0.75 + 100/100
100/100 100/100 15/40 40/35 40/35 31 0.25 4D + 0.75 + 100/100
100/100 100/100 60/40 60/35 60/35 31 0.5 4D + 0.75 + 100/100
100/100 100/100 35/40 30/35 40/35 31 1.0 4D + 0.75 + 75/100 95/100
95/100 5/40 0/35 10/35 15 0.125 4D + 0.75 + 100/100 100/100 100/100
10/40 10/35 15/35 15 0.25 4D + 0 75 + 100/100 100/100 100/100 10/40
10/35 10/35 15 0.5 4D + 0.75 + 100/100 100/100 100/100 5/40 10/35
20/35 15 1.0 RATING 25 DAYS AFTER TREATMENT 4D + 0.75 + 100/70
100/95 99/100 8/15 3/5 3/13 25 0.063 4D + 0.75 + 75/70 95/95 95/100
23/15 18/5 23/13 25 0.125 4D + 0.75 + 98/70 100/95 100/100 23/15
13/5 15/13 25 0.25 4D + 0.75 + 99/70 98/95 98/100 5/15 3/5 8/13 25
0.5 4D + 0.75 + 100/70 99/95 99/100 0/15 0/5 3/13 26 0.063 4D +
0.75 + 100/70 100/95 95/100 13/15 5/5 3/13 26 0.125 4D + 0.75 +
95/70 100/95 98/100 3/15 0/5 28/13 26 0.25 4D + 0.75 + 100/70
100/95 98/100 3/15 0/5 18/13 26 0.5 4D + 0.75 + 75/70 100/95 99/100
13/15 0/5 0/13 27 0.063 4D + 0.75 + 98/70 100/95 100/100 10/15 10/5
13/13 27 0.125 4D + 0.75 + 70/70 99/95 100/100 5/15 13/5 18/13 27
0.25 4D + 0.75 + 100/70 100/95 98/100 15/15 15/5 18/13 27 0.5 4D +
0.75 + 85/70 100/95 98/100 18/15 10/5 13/13 27 0.063 4D + 0.75 +
98/70 95/95 95/100 10/15 13/5 13/13 27 0.125 4D + 0.75 + 80/70
100/95 100/100 28/15 13/5 15/13 27 0.25 4D + 0.75 + 95/70 100/95
100/100 15/15 13/5 13/13 27 0.5 4D + 0.75 + 80/70 88/95 93/100 5/15
8/5 8/13
5 0.167 4D + 0.75 + 98/70 100/95 100/100 10/15 10/5 13/13 5 0.33 4D
+ 0.75 + 100/70 100/95 100/100 18/15 15/5 15/13 5 0.67
__________________________________________________________________________
TABLE V-B
__________________________________________________________________________
RATING 24 DAYS AFTER TREATMENT Rate kg/ha Treatment Herb + Ant.
AMARE SETVI ECHCG CN 64 CN23A C3475
__________________________________________________________________________
24D + 0.28 + 85/95 100/100 100/100 60/75 65/83 95/100 21 0.14 24D +
0.28 + 100/95 100/100 100/100 45/75 55/83 83/100 21 0.28 24D + 0.28
+ 98/95 100/100 100/100 70/75 80/83 95/100 21 0.56 24D + 0.56 +
100/95 100/100 100/100 95/95 100/99 100/100 21 0.14 24D + 0.56 +
83/95 100/100 100/100 68/95 88/99 93/100 21 0.28 24D + 0.56 +
100/95 100/100 100/100 93/95 100/99 100/100 21 0.56 4D + 0.56 +
50/73 100/100 100/100 8/15 10/15 35/23 21 0.14 4D + 0.56 + 73/73
100/100 100/100 18/15 10/15 20/23 21 0.28 4D + 0.56 + 38/73 100/100
100/100 18/15 10/15 18/23 21 0.56 4D + 0.84 + 73/95 100/100 100/100
20/30 23/33 45/45 21 0.14 4D + 0.84 + 63/95 100/100 100/100 20/30
18/33 30/45 21 0.28 4D + 0.84 + 68/95 100/100 100/100 20/30 15/33
25/45 21 0.56
__________________________________________________________________________
TABLES VI, VII, VIII, IX, X, XI
The following compounds were employed as examples of antidotes in
Tables VI, VII, VIII, IX, X and XI, as indicated in the respective
tables.
______________________________________ 18
2,2-dimethyl-3-dichloroacetyl-5-n-propyl oxazolidine 19
3-(dichloroacetyl)-2,2,5-trimethyl thiazolidine 33
2,2-dimethyl-N-dichloroacetyl-5-isopropoxymethyl oxazolidine 25
2,2-dimethyl-3-dichloroacetyl-5-methoxymethyl oxazolidine 26
2,2-dimethyl-3-dichloroacetyl-5-ethoxymethyl oxazolidine 29
2,2-dimethyl-3-dichloroacetyl-5-ethyl-thiomethyl oxazolidine 34
2-2-dimethyl-3-(dichloroacetyl)-5-(ethylsulfonylmethyl)-1-3,
oxazolidine 35 2-methyl-2-carboethoxymethyl-3-dichloroacetyl
thiazolidine 36 2-methyl-2-carbomethoxymethyl-3-dichloroacetyl
thiazolidine 37 2-methyl-2-ethyl-3-dichloroacetyl-1,3-thiazolidine
38 2-butyn-1-yl-p-toluenesulfonyl carbamate 39
2,2,2-trifluoroethyl-p-chlorophenyl carbamate
______________________________________
Procedures for Tables VI, VII, VIII and IX are substantially the
same as given above. Crop seeds and weeds were as follows:
Weed:
SETVI--green foxtail (Sertaria viridis)
ECHCG--watergrass (Echinochloa crusgalli)
AMARE--redroot pigweed (Amaranthus retroflexus)
Crop: Corn Varieties CN64; CN72AA; XL55; CN23A; CN447; CN3475
CN405W; CN7780; CN3541; CN7751; CN22; CN5340; CN8415; CN Golden
Jubiliee (CN GJ) CN6060; CNC6595; CNL17; CNLH74; CNL123; CN179;
CN872; CN59; CN73; CN397; CN4256; CN3535; CN1100.
TABLE VI
__________________________________________________________________________
Rating 29 Days after Treatment Rate Treat- lb/A CN CN CN CN CN CN
ment Herb + Ant. SETVI CN64 72AA XL55 CN23A CN447 ECHOG 3475 405W
7780 3541 7751
__________________________________________________________________________
4D + 0.75 + 100/100 3/20 5/25 3/23 3/18 23/38 100/100 0/10 0/10
0/18 15/38 5/58 2 0.063 4D + 0.75 + 100/100 3/20 18/25 8/23 10/18
3/38 100/100 5/10 13/10 3/18 48/38 8/58 2 0.125 4D + 0.75 + 100/100
5/20 10/25 3/23 4/18 8/38 100/100 0/10 0/10 0/18 68/38 3/58 2 0.25
4D + 0.75 + 100/100 5/20 10/25 3/23 4/18 5/38 100/100 10/10 3/10
8/18 15/38 13/58 6 0.063 4D + 0.75 + 100/100 8/20 20/25 5/23 5/18
5/38 100/100 5/10 10/10 5/18 70/38 18/58 6 0.125 4D + 0.75 +
100/100 10/20 18/25 13/23 8/18 8/38 100/100 5/10 3/10 5/18 0/38
10/58 6 0.25 4D + 0.75 + 100/100 10/20 23/25 0/23 5/18 5/38 100/100
8/10 5/10 8/18 0/38 10/58 6 0.5 4D + 0.75 + 100/100 10/20 25/25
10/23 8/18 15/38 100/100 3/10 5/10 3/18 50/38 3/58 7 0.063 4D +
0.75 + 100/100 3/20 8/25 0/23 5/18 8/38 100/100 0/10 0/10 0/18 0/38
4/58 7 0.125 4D + 0.75 + 100/100 5/20 13/25 5/23 0/18 3/38 100/100
0/10 5/10 5/18 50/38 0/58 7 0.25 4D + 0.75 + 100/100 5/20 0/25 0/23
0/18 5/38 100/100 0/10 0/10 5/18 0/38 0/58 7 0.5 4D + 0.75 +
100/100 8/20 5/25 3/23 3/18 8/38 100/100 0/10 0/10 0/18 0/38 5/58
18 0.063 4D + 0.75 + 100/100 8/20 10/25 8/23 5/18 8/38 100/100 3/10
8/10 18/18 50/38 10/58 18 0.125 4D + 0.75 + 100/100 8/20 23/25
15/23 3/18 3/38 100/100 5/10 5/10 5/18 80/38 5/58 18 0.25 4D + 0.75
+ 100/100 13/20 5/25 0/23 5/18 18/38 100/100 3/10 3/10 8/18 13/38
18/58 18 0.5 4D + 0.75 + 100/100 3/20 13/25 10/23 5/18 3/38 100/100
0/10 0/10 0/18 0/38 3/58 33 0.063 4D + 0.75 + 100/100 0/20 3/25
0/23 0/18 5/38 100/100 3/10 8/10 3/18 50/38 10/58 33 0.125 4D +
0.75 + 100/100 3/20 5/25 3/23 0/18 3/38 100/100 3/10 0/10 0/18 3/38
3/58 33 0.25 4D + 0.75 + 99/100 3/20 5/25 0/23 0/18 8/38 100/100
0/10 3/10 3/18 10/38 5/58 33 0.5 4D + 0.75 + 100/100 0/20
0/25 0/23 0/18 0/38 100/100 3/10 0/10 3/18 0/38 3/58 29 0.063 4D +
0.75 + 100/100 5/20 3/25 0/23 0/18 0/38 100/100 0/10 0/10 0/18 0/38
0/58 29 0.125 4D + 0.75 + 100/100 3/20 0/25 5/23 0/18 8/38 100/100
3/10 0/10 13/18 50/38 3/58 29 0.25 4D + 0.75 + 100/100 5/20 0/25
0/23 3/18 0/38 98/100 3/10 0/10 0/18 0/38 0/58 29 0.5 4D + 0.75 +
100/100 10/20 13/25 5/23 0/18 3/38 100/100 3/10 0/10 3/18 3/38 5/58
34 0.063 4D + 0.75 + 100/100 3/20 23/25 0/23 3/18 3/38 100/100 0/10
3/10 0/18 25/38 10/58 34 0.125 4D + 0.75 + 100/100 10/20 13/25
13/23 3/18 0/38 100/100 3/10 0/10 3/18 0/38 3/58 34 0.25 4D + 0.75
+ 100/100 0/20 0/25 0/23 0/18 0/38 100/100 0/10 10/10 8/18 0/38
3/58 34 0.5
__________________________________________________________________________
TABLE VII
__________________________________________________________________________
Rating 27 Days After Treatment Rate lb/A CN CN CN CN CN CN CN
Treatment Herb + Ant. SETVI CN22 5340 8415 CN GJ ECHOG 6060 C596
L117 LH74 L123
__________________________________________________________________________
4D + 1.0 + 100/99 23/26 18/28 20/42 75/81 100/100 8/15 8/11 13/34
8/23 30/27 2 0.063 4D + 1.0 + 100/99 8/26 3/28 5/42 60/81 100/100
8/15 3/11 13/34 5/23 8/27 2 0.125 4D + 1.0 + 85/99 10/26 10/28
38/42 98/81 100/100 10/15 13/11 15/34 23/23 15/27 2 0.25 4D + 1.0 +
100/99 15/26 13/28 18/42 100/81 100/100 8/15 0/11 10/34 10/23 8/27
7 0.063 4D + 1.0 + 100/99 18/26 28/28 28/42 95/81 100/100 10/15
3/11 25/34 23/23 15/27 7 0.125 4D + 1.0 + 100/99 25/26 20/28 20/42
100/81 100/100 18/15 8/11 18/34 20/23 5/27 7 0.25 4D + 1.0 + 99/99
15/26 23/28 18/42 70/81 100/100 10/15 8/11 13/34 10/23 8/27 9 0.063
4D + 1.0 + 100/99 5/26 5/28 10/42 50/81 100/100 5/15 5/11 8/34 8/23
10/27 9 0.125 4D + 1.0 + 100/99 20/26 8/28 15/42 55/81 100/100
13/15 8/11 15/34 25/23 8/27 9 0.25 4D + 1.0 + 100/99 8/26 3/28
30/42 58/81 100/100 5/15 5/11 3/34 3/23 5/27 33 0.063 4D + 1.0 +
100/99 10/26 18/28 18/42 75/81 100/100 5/15 15/11 8/34 15/23 28/27
33 0.125 4D + 1.0 + 100/99 20/26 18/28 3/42 95/81 100/100 8/15 8/11
13/34 10/23 10/27 33 0.25 4D + 1.0 + 85/99 8/26 8/28 10/42 58/81
100/100 3/15 3/11 3/34 5/23 5/27 29 0.063 4D + 1.0 + 100/99 3/26
3/28 8/42 50/81 100/100 8/15 5/11 8/34 5/23 3/27 29 0.125 4D + 1.0
+ 95/99 5/26 4/28 10/42 75/81 100/100 8/15 5/11 5/34 10/23 8/27 29
0.25 4D + 1.0 + 100/99 15/26 10/28 10/42 45/81 100/100 8/15 3/11
10/34 18/23 25/27 34 0.063 4D + 1.0 + 100/99 13/26 10/28 18/42
75/81 100/100 10/15 0/11 8/34 5/23 5/27 34 0.125 4D + 1.0 + 100/99
8/26 10/28 8/42 28/81 100/100 5/15 5/11 10/34 15/23 15/27 34 0.25
4D + 1.0 + 100/99 38/26 40/28 80/42 100/81 99/100 28/15 13/11 68/34
40/23 53/27 25 0.063 4D + 1.0 + 100/99 35/26 33/28 43/42 99/81
98/100 10/15 13/11 55/34 65/23 65/27 25 0.125 4D + 1.0 + 55/99
38/26 25/28 15/42 50/81 100/100 20/15 8/11 33/34 38/23 43/27 25
0.25
4D + 1.0 + 100/99 30/26 15/28 20/42 25/81 100/100 8/15 5/11 10/34
28/23 35/27 26 0.063 4D + 1.0 + 100/99 15/26 13/28 23/42 90/81
100/100 13/15 3/11 3/34 10/23 30/27 26 0.125 4D + 1.0 + 100/99 8/26
20/28 13/42 88/81 100/100 13/15 13/11 5/34 0/23 20/27 26 0.25 4D +
1.0 + 100/99 33/26 43/28 25/42 45/81 100/100 20/15 15/11 18/34
15/23 38/27 18 0.063 4D + 1.0 + 100/99 35/26 35/28 38/42 80/81
100/100 8/15 10/11 10/34 10/23 35/27 18 0.125 4D + 1.0 + 100/99
28/26 35/28 43/42 100/81 100/100 13/15 5/11 28/34 5/23 25/27 18
0.25 4D + 1.0 + 95/99 8/26 23/28 38/42 88/81 100/100 8/15 3/11
28/34 5/23 33/27 19 0.063 4D + 1.0 + 100/99 30/26 33/28 40/42
100/81 100/100 33/15 18/11 53/34 40/23 40/27 19 0.125 4D + 1.0 +
100/99 50/26 38/28 43/42 95/81 100/100 30/15 15/11 23/34 15/23
53/27 19 0.25
__________________________________________________________________________
TABLE VIII
__________________________________________________________________________
Rating 26 Days After Treatment Rate lb/A CN CN CN CN CN Treatment
Herb/Ant. SETVI 7751 CN179 CN872 CN59 8415 CN73 CN397 4256 3535
1100
__________________________________________________________________________
4D + 1.0 + 100/100 25/35 0/30 0/0 0/5 10/35 0/25 0/10 0/100 0/10
0/20 37 0.063 4D + 1.0 + 100/100 20/35 50/30 0/0 50/5 35/35 40/25
35/10 10/100 10/10 5/20 37 0.125 4D + 1.0 + 100/100 15/35 25/30 5/0
40/5 20/35 15/25 0/10 40/100 10/10 20/20 37 0.25 4D + 1.0 + 100/100
10/35 10/30 0/0 40/5 20/35 50/25 15/10 15/100 15/10 10/20 37 0.5 4D
+ 1.75 + 100/100 10/60 10/70 0/45 75/70 40/100 40/95 0/35 20/50
20/25 10/15 37 0.063 4D + 1.75 + 100/100 25/60 65/70 30/45 70/70
40/100 60/95 30/35 10/50 10/25 15/15 37 0.5
__________________________________________________________________________
TABLE IX
__________________________________________________________________________
Rating 13 Days after Treatment Rate lb/A Treatment Herb + Ant.
AMARE SETVI CN7751 CN8415 CN73 CN179
__________________________________________________________________________
4D + 1.0 + 73/78 100/100 65/88 43/83 50/90 50/90 35 0.063 4D + 1.0
+ 100/78 98/100 55/88 75/83 80/90 80/90 35 0.125 4D + 1.0 + 88/78
100/100 65/88 68/83 75/90 78/90 35 0.25 4D + 1.0 + 93/78 100/100
58/88 58/83 75/90 80/90 36 0.5 4D + 1.0 + 88/78 100/100 85/88 75/83
88/90 85/90 36 0.063 4D + 1.0 + 98/78 100/100 58/88 63/83 85/90
85/90 36 0.125 4D + 1.0 + 95/78 100/100 68/88 40/83 68/90 68/90 36
0.25 4D + 1.0 + 93/78 100/100 43/88 53/83 73/90 75/90 36 0.5
__________________________________________________________________________
Compound IV-13 (original sample) was applied as a pre-emergence
tank-mix with either Compound 1, Compound 2, Compound 9, Compound
13 or Compound 39. The herbicide and/or antidote were applied on
three corn hybrids: (Zea mays), barley, milo, wheat, rice and on
the weeds ELEIN and ABUTH. All compounds were technical and
dissolved in a 60:40 acetone/water rati with 0.5% Tween 20.degree.
added. All seeds were planted 2 cm deep i aluminum flats
(10.times.21.times.6 cm deep); soil type was a sandy loam soil, pH
6.7, containing 0.8% O.M. and 8.95 clay. Soil was fortified with
fertilizer (17-17-17) and Captan 80W.RTM. prior to seeding.
Applications were made with the carrier volume of 25 gal/A. Ratings
were conducted 18 days after treatment.
TABLE X
__________________________________________________________________________
Herbicide + Antidote Compound Rate (lb/A) ML RC201 ELEIN ABUTH
__________________________________________________________________________
IV-13 + 1 0.625 + 0.50 25/40 10/15 20/15 0/15 0.625 + 1.00 25/40
0/15 50/15 50/15 0.625 + 2.00 15/40 0/15 40/15 15/15 0.125 + 0.50
50/65 5/15 20/20 0/20 0.125 + 1.00 70/65 10/15 50/20 35/20 0.125 +
2.00 35/65 0/15 30/20 20/20 IV-13 + 2 0.625 + 0.25 15/40 0/15 20/15
10/15 0.625 + 0.50 20/40 0/15 20/15 15/15 0.625 + 1.00 20/40 0/15
35/15 10/15 0.125 + 0.25 40/65 25/15 40/20 50/20 0.125 + 0.50 65/65
20/15 25/20 0/20 0.125 + 1.00 40/65 30/15 50/20 40/20 IV-13 + 13
0.625 + 0.50 35/40 0/15 40/15 0/15 0.625 + 1.00 35/40 5/15 20/15
5/15 0.625 + 2.00 30/40 0/15 65/15 0/15 0.125 + 0.50 80/65 20/15
60/20 10/20 0.125 + 1.00 60/65 15/15 50/20 15/20 0.125 + 2.00 65/65
25/15 40/20 0/20 IV-13 + 9 0.625 + 0.25 10/40 0/15 10/15 30/15
0.625 + 0.50 15/40 0/15 25/15 0/15 0.625 + 1.00 10/40 0/15 5/15
0/15 0.125 + 0.25 20/65 15/15 65/20 10/20 0.125 + 0.50 60/65 20/15
20/20 25/20 0.125 + 1.00 40/65 30/15 30/20 0/20 IV-13 + 39 0.625 +
0.50 25/40 0/15 20/15 15/15 0.625 + 1.00 20/40 0/15 25/15 0/15
0.625 + 2.00 20/40 0/15 20/15 20/15 0.125 + 0.50 50/65 15/15 30/20
40/20 0.125 + 1.00 60/65 10/15 30/20 30/20 0.125 + 2.00 60/65 20/15
20/20 0/20
__________________________________________________________________________
Herbicide + Antidote CORN Compound Rate (lb/A) ELEIN ABUTH AVERAGE
BARLEY WHEAT
__________________________________________________________________________
IV-13 + 1 0.50 + 0.50 95/88 100/95 0/0 0/0 10/5 0.50 + 1.00 90/88
100/95 0/0 0/0 25/5 0.50 + 2.00 80/88 90/95 0/0 0/0 5/5 1.00 + 0.50
100/98 100/93 0/0 0/0 10/10 1.00 + 1.00 100/98 100/93 0/0 0/0 5/10
1.00 + 2.00 85/98 85/93 0/0 0/0 5/10 IV-13 + 2 0.50 + 0.25 85/88
95/95 0/0 0/0 0/5 0.50 + 0.50 98/88 100/95 0/0 0/0 10/5 0.50 + 1.00
98/88 100/95 0/0 0/0 15/5 1.00 + 0.25 98/98 100/93 0/0 0/0 5/10
1.00 + 0.50 80/98 100/93 0/0 0/0 5/10 1.00 + 1.00 98/98 100/93 0/0
0/0 10/10 IV-13 + 13 0.50 + 0.50 95/88 100/95 0/0 0/0 10/5 0.50 +
1.00 90/88 100/95 0/0 0/0 15/5 0.50 + 2.00 90/88 100/95 0/0 0/0
20/5 1.00 + 0.50 75/98 100/93 0/0 0/0 10/10 1.00 + 1.00 90/98
100/93 0/0 0/0 15/10 1.00 + 2.00 70/98 90/93 0/0 0/0 10/10 IV-13 +
9 0.50 + 0.25 85/88 100/95 0/0 0/0 10/5 0.50 + 0.50 90/88 100/95
0/0 0/0 10/5 0.50 + 1.00 95/88 100/95 0/0 0/0 5/5 1.00 + 0.25 85/98
100/93 0/0 0/0 5/10 1.00 + 0.50 90/98 100/93 0/0 0/0 15/10 1.00 +
1.00 95/98 100/93 0/0 0/0 5/10 IV-13 + 39 0.50 + 0.50 95/88 100/95
0/0 0/0 0/5 0.50 + 1.00 85/88 100/95 0/0 0/0 10/5 0.50 + 2.00 75/88
100/95 0/0 0/0 20/5 1.00 + 0.50 100/98 100/93 0/0 0/0 25/10 1.00 +
1.00 90/98 100/93 0/0 0/0 5/10 1.00 + 2.00 85/98 100/93 0/0 0/0
10/10
__________________________________________________________________________
TABLE XI ______________________________________ Herbicide +
Antidote Average Corn* Compound Rate (lb/A) SETVI BL* ST
______________________________________ Early Rating 71D + 2 0.125 +
0.125 100/100 60/58 15/26 0.125 + 0.250 100/100 39/58 13/26 0.125 +
0.500 100/100 16/58 11/26 0.250 + 0.125 100/100 68/41 29/14 0.250 +
0.250 100/100 65/41 33/14 0.250 + 0.500 100/100 63/41 31/14 71D + 9
0.125 + 0.125 100/100 0/58 0/26 0.125 + 0.250 100/100 40/58 20/26
0.125 + 0.500 100/100 15/58 10/26 0.250 + 0.125 100/100 35/41 16/14
0.250 + 0.250 100/100 53/41 19/14 0.250 + 0.500 100/100 64/41 30/14
71D + 29 0.125 + 0.125 95/100 11/58 9/26 0.125 + 0.250 100/100
39/58 19/26 0.125 + 0.500 95/100 6/58 5/26 0.250 + 0.125 100/100
35/41 16/14 0.250 + 0.250 100/100 40/41 26/14 0.250 + 0.500 100/100
45/41 33/14 Late Rating 71D + 2 0.125 + 0.125 100/100 15/3 25/49
0.125 + 0.250 100/100 19/3 23/49 0.125 + 0.500 100/100 9/3 21/49
0.250 + 0.125 100/100 4/8 55/9 0.250 + 0.250 100/100 9/8 30/9 0.250
+ 0.500 100/100 0/8 45/9 71D + 9 0.125 + 0.125 100/100 0/3 0/49
0.125 + 0.250 100/100 1/3 0/49 0.125 + 0.500 100/100 10/3 16/49 71D
+ 9 0.250 + 0.125 100/100 11/8 23/9 0.250 + 0.250 100/100 9/8 16/9
0.250 + 0.500 100/100 4/8 44/9 71D + 29 0.125 + 0.125 90/100 3/3
11/49 0.125 + 0.250 100/100 0/3 0/49 0.125 + 0.500 95/100 0/3 10/49
71d + 29 0.250 + 0.125 95/100 9/8 16/9 0.250 + 0.250 100/100 6/8
23/9 0.250 + 0.500 100/100 14/8 35/9
______________________________________ BL = Bleaching ST =
Stunting
TABLE XII
__________________________________________________________________________
Seed Treatment
__________________________________________________________________________
Herbicides: 8D and 51A Antidote: Compound 32 Antidote was applied
as a seed treatment (0.0625% to 0.5% of the antidote by weight of
the seed) Planting was 2 cm deep in sandy loam soil. Ratings were
conducted 12 days after treatment and 21 days after treatment. Two
weed species: ABUTH velvetleaf (Abutilon theophrasti) ELEIN
goodgrass (Eleusine indica) Corn varieties: Corn 3737 Corn 7751
Average represents average valued for bleaching (BL) and stunting
__________________________________________________________________________
(ST). Herbicide-Antidote Time Rate Average Corn Compounds (days)
(lb/A + w/w %) ELEIN ABUTH BL ST
__________________________________________________________________________
8D 32 12 0.5 + 0.5% 100/100 100/100 0/40 10/20 21 0.5 + 0.5%
100/100 100/100 0/20 10/33 CN 7751 51A 32 20 1.0 + 0.5% 100/100
100/100 0/18
__________________________________________________________________________
FORMULATIONS
A formulation is the incorporation of a formulant in a form which
is directly usable on crops and weeds. As defined herein, a
"formulant" is the material which is to be formulated. The
formulant may be either an antidote compound alone or an herbicide
and antidote composition. The purpose of the formulation is to
apply the formulant to the locus of a crop where it is desired to
establish herbicidal selectivity by a convenient method. The
"locus" may include soil, seeds, crop, crop seeds, seedlings and
vegetation.
The antidotes described herein can be formulated in a number of
ways for suitable application: (a) the antidote can be formulated
for application directly to the crop seed; (b) the antidote and
herbicide may be formulated separately and applied separately or
applied simultaneously in an appropriate weight ratio, e.g., as a
tank mix, or (c) the antidote and herbicide may be formulated
together in the proper weight ratio.
Useful formulations of the compounds of this invention can be
prepared in conventional ways. They include dusts, granules,
microcapsules, pellets, solutions, suspensions, emulsions, wettable
powders, emulsifiable concentrates and the like. Many of these may
be applied directly to the locus. Sprayable formulations can be
extended in suitable media and used at spray volumes of from a few
liters to several hundred liters per hectare. High strength
compositions are primarily used as intermediates for further
formulation. The formulations, broadly, contain about 0.1% to 99%
by weight of active herbicide and antidote ingredient(s) and at
least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1%
to 99.9% solid or liquid inert diluent(s). More specifically, they
can contain these ingredients in the following approximate
proportions.
TABLE 2 ______________________________________ Active Herb &
Ant. Weight Percent* Ingredients Diluent(s) Surfactant(s)
______________________________________ Wettable Powders 20-90 0-74
1-10 Oil Suspensions 3-50 40-95 0-15 Emulsions, Solutions,
(including Emulsifiable Concentrates) Aqueous Suspension 10-50
40-84 1-20 Dusts 1-25 70-99 0-5 Granules and Pellets 0.1-95 5-99.9
0-15 High Strength 90-99 0-10 0-2 Compositions
______________________________________ *Active ingredient plus at
least one of a Surfactant or a Diluent equals 100 weight
percent.
Lower or higher levels of active ingredient can, of course, be
present depending on the intended use and the physical properties
of the compound. Higher ratios of surfactant to active ingredient
are sometimes desirable, and are achieved by incorporation into the
formula or by tank mixing.
Dusts are free-flowing powder compositions containing the formulant
impregnated on a particulate carrier. The particle size of the
carriers is usually in the approximate range of 30 to 50 microns.
Examples of suitable carriers are talc, bentonite, diatomaceous
earth, and pyrophyllite. The composition generally contains up to
50% of formulant. Anti-caking and anti-static agents may also be
added. Dusts may be applied by spraying from boom sprayers, hand
sprayers or airplanes.
Wettable powders are finely divided compositions comprising a
particular carrier impregnated with the formulant and additionally
containing one or more surface active agents. The surface active
agent promotes rapid dispersion of the powder in an aqueous medium
to form stable, sprayable suspensions. A wide variety of surface
active agents can be used, for example, long chain fatty alcohols
and alkali metal salts of the sulfated fatty alcohols; salts of
sulfonic acid; esters of long chain fatty acids; and polyhydric
alcohols, in which the alcohol groups are free, omega-substituted
polyethylene glycols of relatively long chain length. A list of
surface active agents suitable for use in agriculture formulations
can be found in Wade Van Valkenburg, Pesticide Formulations (Mercel
Dekker, Inc., N.Y., 1973) at pages 79-84.
Granules comprise the formulant impregnated on a particulate inert
carrier having a particle size of about 1 to 2 millimeters (mm) in
diameter. The granules can be made by spraying a solution of the
formulant in a volatile solvent onto the granular carrier. Examples
of suitable carriers for the preparation of granules include clay,
vermiculite sawdust, and granular carbon.
Microcapsules and other slow release formulations are advantageous
as formulations to deliver and distribute the active ingredients.
Microcapsules consist of fully enclosed droplets or granules
containing the active materials in which the enclosing material is
an inert porous membrane, arranged to allow escape of the enclosed
materials to the surrounding medium at controlled rates over a
specified period of time. Encapsulated droplets are typically about
1 to 50 microns in diameter. The enclosed liquid typically
constitutes about 50 to 90% of the weight of the entire capsule,
and may contain an amount of solvent in addition to the active
materials. Encapsulated granules are characterized by porous
membranes sealing the openings of the granule carrier press,
trapping the liquid containing the active components inside for
controlled release. A typical granule size ranges from 1 millimeter
to 1 centimeter in diameter. In agricultural usage, the granule
size is generally about 1 to 2 millimeters in diameter. Granules
formed by extrusion, agglomeration or prilling are useful in the
present invention as well as materials in their naturally occurring
form. Examples of such carriers are vermiculite, sintered clay
granules, kaolin, attapulgite clay, sawdust and granular carbon.
Useful encapsulating materials include natural and synthetic
rubbers, cellulosic materials, styrene-butadiene copolymers,
polyacrylonitriles, polyacrylates, polyesters, polyamides,
polyureas, polyurethanes and starch xanthates.
Emulsifiable concentrates consist of an oil solution of the
formulant plus an emulsifying agent. Prior to use, the concentrate
is diluted with water to form a suspended emulsion of oil droplets.
The emulsifiers used are usually a mixture of anionic and nonionic
surfactants. Other additives, such as suspending agents and
thickeners, may be included in the emulsifiable concentrate.
When the formulant is an antidote and herbicide composition, the
proportion of antidote compound to herbicide compound generally
ranges from approximately 0.001 to 30 parts by weight of the
antidote compound per weight of the herbicide compound.
Formulations generally contain seveal additives in addition to the
formulant and carrier or agent. Among these are inert ingredients,
diluent carriers, organic solvents, water, oil and water, water in
oil emulsions, carriers of dusts and granules, and surface active
wetting, dispersing and emulsifying agents. Fertilizers, e.g.,
ammonium nitrate urea and superphosphate, may be included. Aids to
rooting and growth, e.g., compost, manure, humus and sand, may also
be included.
Alternatively, the antidote compounds and herbicide and antidote
compositions of this invention can be applied to a crop by addition
of the formulant to irrigation water supplied to the field to be
treated. This method of application permits the penetration of the
compositions into the soil as the water is absorbed.
As another alternative, the formulant can be applied to the soil in
the form of a solution in a suitable solvent. Solvents frequently
used in these formulations include kerosene, fuel oil, xylene,
petroleum fractions with boiling ranges above xylene and aromatic
petroleum fractions rich in methylated naphthalenes. Liquid
solutions, like dusts, may be applied by spraying from boom and
hand sprayers or airplanes.
EXAMPLE
Dusts: The following substances are used to formulate (a) 5% and
(b) a 2% dust:
(a)
5 parts of active substance
95 parts of talc;
(b)
2 parts of active substance
1 part of highly dispersed silicic acid
97 parts of talc.
The active substances are mixed with the carriers and ground and in
this form can be processed to dusts for application.
EXAMPLE
Granulate: The following substances are used to formulate a 5%
granulate:
5 parts of active substance
0.25 part of epichlorohydrin
0.25 part of cetyl polyglycol ether
3.25 parts of polyethylene glycol
91 parts of kaolin (particle size 0.3-0.8 mm).
The active substance is mixed with epichlorohydrin and the mixture
is dissolved in 6 parts of acetone. Then polyethylene glycol and
cetyl polyglycol ether are added. The resultant solution is sprayed
on kaolin and the acetone is evaporated in vacuo.
EXAMPLE
Wettable powders: The following constituents are used to formula
(a) a 70%, (b) a 40%, (c) and (d) a 25% and (e) a 10% wettable
powder.
(a)
70 parts of active substance
5 parts of sodium dibutylnaphthylsulfonate
3 parts of naphthalenesulfonic acid/phenolsulfonic
acid/formaldehyde condensate (3:2:1)
10 parts of kaolin
12 parts of Champagne chalk
(b)
40 parts of active substance
5 parts of sodium ligninsulfonate
1 part of sodium dibutylnaphthalenesulfonic acid
54 parts of silicic acid
(c)
25 parts of active substance
4.5 parts of calcium ligninsulfate
1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture
(1:1)
1.5 parts of sodium dibutylnaphthalenesulfonate
19.5 parts of silicic acid
19.5 parts of Champagne chalk
28.1 parts of kaolin
(d)
25 parts of active substance
2.5 parts of isoctylphenoxy-polyethylene-ethanol
1.7 parts of a Champagne chalk/hydroxyethyl cellulose mixture
(1:1)
8.3 parts of sodium aluminum silicate
16.5 parts of kieselguhr
46 parts of kaolin
(e)
10 parts of active substance
3 parts of a mixture of the sodium salts of saturated fatty alcohol
sulfates
5 parts of naphthalenesulfonic acid/formaldehyde condensate
82 parts of kaolin.
The active substances are intimately mixed in suitable mixers with
the additives and ground in appropriate mills and rollers. Wettable
powders of excellent wettability and suspension power are obtained.
These wettable powders can be diluted with water to give
suspensions of the desired concentration and can be used in
particular for treating parts of plants.
EXAMPLE
Emulsifiable concentrate: The following substances are used to
formulate a 25% emulsifiable concentrate:
25 parts of active substance
2.5 parts of epoxidized vegetable oil
10 parts of an alkylarylsulfonate/fatty alcohol polyglycol ether
mixture
5 parts of dimethylformamide
57.5 parts of xylene.
By diluting such a concentrate with water it is possible to prepare
emulsions of the desired concentrations, which are especially
suitable for leaf application.
* * * * *